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Clouds affect the Earth climate with an impact that depends on the cloud nature (solid and/or liquid water). Although the Antarctic climate is changing rapidly, cloud observations are sparse over Antarctica due to few ground stations and satellite observations. The Concordia station is located on the eastern Antarctic Plateau (75∘ S, 123∘ E; 3233 m above mean sea level), one of the driest and coldest places on Earth. We used observations of clouds, temperature, liquid water, and surface irradiance performed at Concordia during four austral summers (December 2018–2021) to analyse the link between liquid water and temperature and its impact on surface irradiance in the presence of supercooled liquid water (liquid water for temperature less than 0 ∘C) clouds (SLWCs). Our analysis shows that, within SLWCs, temperature logarithmically increases from −36.0 to −16.0 ∘C when liquid water path increases from 1.0 to 14.0 g m−2. The SLWC radiative forcing is positive and logarithmically increases from 0.0 to 70.0 W m−2 when liquid water path increases from 1.2 to 3.5 g m−2. This is mainly due to the downward longwave component that logarithmically increases from 0 to 90 W m−2 when liquid water path increases from 1.0 to 3.5 g m−2. The attenuation of shortwave incoming irradiance (that can reach more than 100 W m−2) is almost compensated for by the upward shortwave irradiance because of high values of surface albedo. Based on our study, we can extrapolate that, over the Antarctic continent, SLWCs have a maximum radiative forcing that is rather weak over the eastern Antarctic Plateau (0 to 7 W m−2) but 3 to 5 times larger over West Antarctica (0 to 40 W m−2), maximizing in summer and over the Antarctic Peninsula.

A comprehensive analysis of the water budget over the Dome C (Concordia, Antarctica) station has been performed during the austral summer 2018–2019 as part of the Year of Polar Prediction (YOPP) international campaign. Thin (∼100 m deep) supercooled liquid water (SLW) clouds have been detected and analysed using remotely sensed observations at the station (tropospheric depolarization lidar, the H2O Antarctica Microwave Stratospheric and Tropospheric Radiometer (HAMSTRAD), net surface radiation from the Baseline Surface Radiation Network (BSRN)), radiosondes, and satellite observations (CALIOP, Cloud-Aerosol LIdar with Orthogonal Polarization/CALIPSO, Cloud Aerosol Lidar and Infrared Pathfinder Satellite Observations) combined with a specific configuration of the numerical weather prediction model: ARPEGE-SH (Action de Recherche Petite Echelle Grande Echelle – Southern Hemisphere). The analysis shows that SLW clouds were present from November to March, with the greatest frequency occurring in December and January when ∼50 % of the days in summer time exhibited SLW clouds for at least 1 h. Two case studies are used to illustrate this phenomenon. On 24 December 2018, the atmospheric planetary boundary layer (PBL) evolved following a typical diurnal variation, which is to say with a warm and dry mixing layer at local noon thicker than the cold and dry stable layer at local midnight. Our study showed that the SLW clouds were observed at Dome C within the entrainment and the capping inversion zones at the top of the PBL. ARPEGE-SH was not able to correctly estimate the ratio between liquid and solid water inside the clouds with the liquid water path (LWP) strongly underestimated by a factor of 1000 compared to observations. The lack of simulated SLW in the model impacted the net surface radiation that was 20–30 W m−2 higher in the BSRN observations than in the ARPEGE-SH calculations, mainly attributable to the BSRN longwave downward surface radiation being 50 W m−2 greater than that of ARPEGE-SH. The second case study took place on 20 December 2018, when a warm and wet episode impacted the PBL with no clear diurnal cycle of the PBL top. SLW cloud appearance within the entrainment and capping inversion zones coincided with the warm and wet event. The amount of liquid water measured by HAMSTRAD was ∼20 times greater in this perturbed PBL than in the typical PBL. Since ARPEGE-SH was not able to accurately reproduce these SLW clouds, the discrepancy between the observed and calculated net surface radiation was even greater than in the typical PBL case, reaching +50 W m−2, mainly attributable to the downwelling longwave surface radiation from BSRN being 100 W m−2 greater than that of ARPEGE-SH. The model was then run with a new partition function favouring liquid water for temperatures below −20 down to −40 ∘C. In this test mode, ARPEGE-SH has been able to generate SLW clouds with modelled LWP and net surface radiation consistent with observations during the typical case, whereas, during the perturbed case, the modelled LWP was 10 times less than the observations and the modelled net surface radiation remained lower than the observations by ∼50 W m−2. Accurately modelling the presence of SLW clouds appears crucial to correctly simulate the surface energy budget over the Antarctic Plateau.

We present an Observing System Simulation Experiment (OSSE) dedicated to the evaluation of the added value of the Sentinel-4 and Sentinel-5P missions for tropospheric nitrogen dioxide (NO2). Sentinel-4 is a geostationary (GEO) mission covering the European continent, providing observations with high temporal resolution (hourly). Sentinel-5P is a low Earth orbit (LEO) mission providing daily observations with a global coverage. The OSSE experiment has been carefully designed, with separate models for the simulation of observations and for the assimilation experiments and with conservative estimates of the total observation uncertainties. In the experiment we simulate Sentinel-4 and Sentinel-5P tropospheric NO2 columns and surface ozone concentrations at 7 by 7 km resolution over Europe for two 3-month summer and winter periods. The synthetic observations are based on a nature run (NR) from a chemistry transport model (MOCAGE) and error estimates using instrument characteristics. We assimilate the simulated observations into a chemistry transport model (LOTOS-EUROS) independent of the NR to evaluate their impact on modelled NO2 tropospheric columns and surface concentrations. The results are compared to an operational system where only ground-based ozone observations are ingested. Both instruments have an added value to analysed NO2 columns and surface values, reflected in decreased biases and improved correlations. The Sentinel-4 NO2 observations with hourly temporal resolution benefit modelled NO2 analyses throughout the entire day where the daily Sentinel-5P NO2 observations have a slightly lower impact that lasts up to 3–6 h after overpass. The evaluated benefits may be even higher in reality as the applied error estimates were shown to be higher than actual errors in the now operational Sentinel-5P NO2 products. We show that an accurate representation of the NO2 profile is crucial for the benefit of the column observations on surface values. The results support the need for having a combination of GEO and LEO missions for NO2 analyses in view of the complementary benefits of hourly temporal resolution (GEO, Sentinel-4) and global coverage (LEO, Sentinel-5P).

The contribution of deep convection to the amount of water vapour and ice in the tropical tropopause layer (TTL) from the tropical upper troposphere (UT; around 146 hPa) to the tropopause level (TL; around 100 hPa) is investigated. Ice water content (IWC) and water vapour (WV) measured in the UT and the TL by the Microwave Limb Sounder (MLS; Version 4.2) are compared to the precipitation (Prec) measured by the Tropical Rainfall Measurement Mission (TRMM; Version 007). The two datasets, gridded within 2∘ × 2∘ horizontal bins, have been analysed during the austral convective season, December, January, and February (DJF), from 2004 to 2017. MLS observations are performed at 01:30 and 13:30 local solar time, whilst the Prec dataset is constructed with a time resolution of 1 h. The new contribution of this study is to provide a much more detailed picture of the diurnal variation of ice than is provided by the very limited (two per day) MLS observations. Firstly, we show that IWC represents 70 % and 50 % of the total water in the tropical UT and TL, respectively, and that Prec is spatially highly correlated with IWC in the UT (Pearson's linear coefficient R=0.7). We propose a method that uses Prec as a proxy for deep convection bringing ice up to the UT and TL during the growing stage of convection, in order to estimate the amount of ice injected into the UT and the TL, respectively. We validate the method using ice measurements from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) during the period DJF 2009–2010. Next, the diurnal cycle of injection of IWC into the UT and the TL by deep convection is calculated by the difference between the maximum and the minimum in the estimated diurnal cycle of IWC in these layers and over selected convective zones. Six tropical highly convective zones have been chosen: South America, South Africa, Pacific Ocean, Indian Ocean, and the Maritime Continent region, split into land (MariCont-L) and ocean (MariCont-O). IWC injection is found to be 2.73 and 0.41 mg m−3 over tropical land in the UT and TL, respectively, and 0.60 and 0.13 mg m−3 over tropical ocean in the UT and TL, respectively. The MariCont-L region has the greatest ice injection in both the UT and TL (3.34 and 0.42–0.56 mg m−3, respectively). The MariCont-O region has less ice injection than MariCont-L (0.91 mg m−3 in the UT and 0.16–0.34 mg m−3 in TL) but has the highest diurnal minimum value of IWC in the TL (0.34–0.37 mg m−3) among all oceanic zones.

In the framework of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx; http://charmex.lsce.ipsl.fr, last access: 22 June 2018) project, we study the evolution of surface ozone over the Mediterranean Basin (MB) with a focus on summertime over the time period 2000–2100, using the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) outputs from 13 models. We consider three different periods (2000, 2030 and 2100) and the four Representative Concentration Pathways (RCP2.6, RCP4.5, RCP6.0 and RCP8.5) to study the changes in the future ozone and its budget. We use a statistical approach to compare and discuss the results of the models. We discuss the behavior of the models that simulate the surface ozone over the MB. The shape of the annual cycle of surface ozone simulated by ACCMIP models is similar to the annual cycle of the ozone observations, but the model values are biased high. For the summer, we found that most of the models overestimate surface ozone compared to observations over the most recent period (1990–2010). Compared to the reference period (2000), we found a net decrease in the ensemble mean surface ozone over the MB in 2030 (2100) for three RCPs: −14 % (−38 %) for RCP2.6, −9 % (−24 %) for RCP4.5 and −10 % (−29 %) for RCP6.0. The surface ozone decrease over the MB for these scenarios is much more pronounced than the relative changes of the global tropospheric ozone burden. This is mainly due to the reduction in ozone precursors and to the nitrogen oxide (NOx = NO + NO2)-limited regime over the MB. For RCP8.5, the ensemble mean surface ozone is almost constant over the MB from 2000 to 2100. We show how the future climate change and in particular the increase in methane concentrations can offset the benefits from the reduction in emissions of ozone precursors over the MB.

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 eastern Mediterranean (EM) is one of the regions in the world where elevated concentrations of primary and secondary gaseous air pollutants have been reported frequently, mainly in summer. This review discusses published studies of the atmospheric dispersion and transport conditions characterizing this region during the summer, followed by a description of some essential studies dealing with the corresponding concentrations of air pollutants such as ozone, carbon monoxide, total reactive nitrogen, methane, and sulfate aerosols observed there. The interlaced relationship between the downward motion of the subsiding air aloft induced by global circulation systems affecting the EM and the depth of the Persian Trough, a low-pressure trough that extends from the Asian monsoon at the surface controlling the spatiotemporal distribution of the mixed boundary layer during summer, is discussed. The strength of the wind flow within the mixed layer and its depth affect much the amount of pollutants transported and determine the potential of the atmosphere to disperse contaminants off their origins in the EM. The reduced mixed layer and the accompanying weak westerlies, characterizing the summer in this region, led to reduced ventilation rates, preventing an effective dilution of the contaminants. Several studies pointing at specific local (e.g., ventilation rates) and regional peculiarities (long-range transport) enhancing the build-up of air pollutant concentrations are presented. Tropospheric ozone (O3) concentrations observed in the summer over the EM are among the highest over the Northern Hemisphere. The three essential processes controlling its formation (i.e., long-range transport of polluted air masses, dynamic subsidence at mid-tropospheric levels, and stratosphere-to-troposphere exchange) are reviewed. Airborne campaigns and satellite-borne initiatives have indicated that the concentration values of reactive nitrogen identified as precursors in the formation of O3 over the EM were found to be 2 to 10 times higher than in the hemispheric background troposphere. Several factors favor sulfate particulate abundance over the EM. Models, aircraft measurements, and satellite-derived data have clearly shown that sulfate has a maximum during spring and summer over the EM. The carbon monoxide (CO) seasonal cycle, as obtained from global background monitoring sites in the EM, is mostly controlled by the tropospheric concentration of the hydroxyl radical (OH) and therefore demonstrates high concentrations over winter months and the lowest concentrations during summer when photochemistry is active. Modeling studies have shown that the diurnal variations in CO concentration during the summer result from long-range CO transport from European anthropogenic sources, contributing 60 to 80 % of the boundary-layer CO over the EM. The values retrieved from satellite data enable us to derive the spatial distribution of methane (CH4), identifying August as the month with the highest levels over the EM. The outcomes of a recent extensive examination of the distribution of methane over the tropospheric Mediterranean Basin, as part of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx) program, using model simulations and satellite measurements, are coherent with other previous studies. Moreover, this methane study provides some insight into the role of the Asian monsoon anticyclone in controlling the variability of CH4 pollutant within mid-to-upper tropospheric levels above the EM in summer.

Episodes of thick cloud and diamond dust/ice fog were observed during 15 March to 8 April 2011 and 4 to 5 March 2013 in the atmosphere above Dome C (Concordia station, Antarctica; 75°06′ S, 123°21′ E; 3233 m a.m.s.l.). The objectives of the paper are mainly to investigate the processes that cause these episodes based on observations and to verify whether operational models can evaluate them. The measurements were obtained from the following instruments: (1) a ground-based microwave radiometer (HAMSTRAD, H2O Antarctica Microwave Stratospheric and Tropospheric Radiometers) installed at Dome C that provided vertical profiles of tropospheric temperature and absolute humidity every 7 min; (2) daily radiosoundings launched at 12:00 UTC at Dome C; (3) a tropospheric aerosol lidar that provides aerosol depolarization ratio along the vertical at Dome C; (4) down- and upward short- and long-wave radiations as provided by the Baseline Surface Radiation Network (BSRN) facilities; (5) an ICE-CAMERA to detect at an hourly rate the size of the ice crystal grains deposited at the surface of the camera; and (6) space-borne aerosol depolarization ratio from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) lidar aboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) platform along orbits close to the Dome C station. The time evolution of the atmosphere has also been evaluated by considering the outputs from the mesoscale AROME and the global-scale ARPEGE meteorological models. Thick clouds are detected during the warm and wet periods (24–26 March 2011 and 4 March 2013) with high depolarization ratios (greater than 30 %) from the surface to 5–7 km above the ground associated with precipitation of ice particles and the presence of a supercooled liquid water (depolarization less than 10 %) clouds. Diamond dust and/or ice fog are detected during the cold and dry periods (5 April 2011 and 5 March 2013) with high depolarization ratios (greater than 30 %) in the planetary boundary layer to a maximum altitude of 100–300 m above the ground with little trace of precipitation. Considering 5-day back trajectories, we show that the thick cloud episodes are attributed to air masses with an oceanic origin whilst the diamond dust/ice fog episodes are attributed to air masses with continental origins. Although operational models can reproduce thick cloud episodes in the free troposphere, they cannot evaluate the diamond dust/ice fog episodes in the planetary boundary layer because they require to use more sophisticated cloud and aerosol microphysics schemes.

We use the technique of Observing System Simulation Experiments (OSSEs) to quantify the impact of spaceborne carbon monoxide (CO) total column observations from the Sentinel-5 Precursor (S-5P) platform on tropospheric analyses and forecasts. We focus on Europe for the period of northern summer 2003, when there was a severe heat wave episode associated with extremely hot and dry weather conditions. We describe different elements of the OSSE: (i) the nature run (NR), i.e., the truth; (ii) the CO synthetic observations; (iii) the assimilation run (AR), where we assimilate the observations of interest; (iv) the control run (CR), in this study a free model run without assimilation; and (v) efforts to establish the fidelity of the OSSE results. Comparison of the results from AR and the CR, against the NR, shows that CO total column observations from S-5P provide a significant benefit (at the 99 % confidence level) at the surface, with the largest benefit occurring over land in regions far away from emission sources. Furthermore, the S-5P CO total column observations are able to capture phenomena such as the forest fires that occurred in Portugal during northern summer 2003. These results provide evidence of the benefit of S-5P observations for monitoring processes contributing to atmospheric pollution.

Under the framework of the GMOS project (Global Mercury Observation System) atmospheric mercury monitoring has been implemented at Concordia Station on the high-altitude Antarctic plateau (75°06′ S, 123°20′ E, 3220 m above sea level). We report here the first year-round measurements of gaseous elemental mercury (Hg(0)) in the atmosphere and in snowpack interstitial air on the East Antarctic ice sheet. This unique data set shows evidence of an intense oxidation of atmospheric Hg(0) in summer (24-hour daylight) due to the high oxidative capacity of the Antarctic plateau atmosphere in this period of the year. Summertime Hg(0) concentrations exhibited a pronounced daily cycle in ambient air with maximal concentrations around midday. Photochemical reactions and chemical exchange at the air–snow interface were prominent, highlighting the role of the snowpack on the atmospheric mercury cycle. Our observations reveal a 20 to 30 % decrease of atmospheric Hg(0) concentrations from May to mid-August (winter, 24 h darkness). This phenomenon has not been reported elsewhere and possibly results from the dry deposition of Hg(0) onto the snowpack. We also reveal the occurrence of multi-day to weeklong atmospheric Hg(0) depletion events in summer, not associated with depletions of ozone, and likely due to a stagnation of air masses above the plateau triggering an accumulation of oxidants within the shallow boundary layer. Our observations suggest that the inland atmospheric reservoir is depleted in Hg(0) in summer. Due to katabatic winds flowing out from the Antarctic plateau down the steep vertical drops along the coast and according to observations at coastal Antarctic stations, the striking reactivity observed on the plateau most likely influences the cycle of atmospheric mercury on a continental scale.

The space and time variabilities of methane (CH4) total column and upper tropospheric mixing ratios are analysed above the Mediterranean Basin (MB) as part of the Chemical and Aerosol Mediterranean Experiment (ChArMEx) programme. Since the analysis of the mid-to-upper tropospheric CH4 distribution from spaceborne sensors and model outputs is challenging, we have adopted a climatological approach and have used a wide variety of data sets. We have combined spaceborne measurements from the Thermal And Near infrared Sensor for carbon Observations – Fourier Transform Spectrometer (TANSO-FTS) instrument on the Greenhouse gases Observing SATellite (GOSAT) satellite, the Atmospheric InfraRed Spectrometer (AIRS) on the AURA platform and the Infrared Atmospheric Sounder Interferometer (IASI) instrument aboard the MetOp-A platform with model results from the Chemical Transport Model (CTM) MOCAGE, and the Chemical Climate Models (CCMs) CNRM-AOCCM and LMDz-OR-INCA (according to different emission scenarios). In order to minimize systematic errors in the spaceborne measurements, we have only considered maritime pixels over the MB. The period of interest spans from 2008 to 2011 considering satellite and MOCAGE data and, regarding the CCMs, from 2001 to 2010. Although CH4 is a long-lived tracer with lifetime of ~12 years and is supposed to be well mixed in the troposphere, an east–west gradient in CH4 is observed and modelled in the mid-to-upper troposphere with a maximum in the Western MB in all seasons except in summer when CH4 accumulates above the Eastern MB. The peak-to-peak amplitude of the east–west seasonal variation in CH4 above the MB in the upper troposphere (300 hPa) is weak but almost twice as great in the satellite measurements (~25 ppbv) as in the model data (~15 ppbv). The maximum of CH4 in summer above the eastern MB can be explained by a series of dynamical processes only occurring in summer. The Asian monsoon traps and uplifts high amounts of CH4 to the upper troposphere where they build up. The Asian Monsoon Anticyclone redistributes these elevated CH4 amounts towards North Africa and the Middle East to finally reach and descend in the eastern MB. In the lower troposphere, the CH4 variability is mainly driven by the local sources of emission in the vicinity of the MB.

The tropical deep overshooting convection is known to be most intense above continental areas such as South America, Africa, and the maritime continent. However, its impact on the tropical tropopause layer (TTL) at global scale remains debated. In our analysis, we use the 8-year Microwave Limb Sounder (MLS) water vapour (H2O), cloud ice-water content (IWC), and temperature data sets from 2005 to date, to highlight the interplays between these parameters and their role in the water vapour variability in the TTL, and separately in the northern and southern tropics. In the tropical upper troposphere (177 hPa), continents, including the maritime continent, present the night-time (01:30 local time, LT) peak in the water vapour mixing ratio characteristic of the H2O diurnal cycle above tropical land. The western Pacific region, governed by the tropical oceanic diurnal cycle, has a daytime maximum (13:30 LT). In the TTL (100 hPa) and tropical lower stratosphere (56 hPa), South America and Africa differ from the maritime continent and western Pacific displaying a daytime maximum of H2O. In addition, the relative amplitude between day and night is found to be systematically higher by 5–10% in the southern tropical upper troposphere and 1–3% in the TTL than in the northern tropics during their respective summer, indicative of a larger impact of the convection on H2O in the southern tropics. Using a regional-scale approach, we investigate how mechanisms linked to the H2O variability differ in function of the geography. In summary, the MLS water vapour and cloud ice-water observations demonstrate a clear contribution to the TTL moistening by ice crystals overshooting over tropical land regions. The process is found to be much more effective in the southern tropics. Deep convection is responsible for the diurnal temperature variability in the same geographical areas in the lowermost stratosphere, which in turn drives the variability of H2O.

The objective of this paper is to deliver the most accurate ozone (O3) and carbon monoxide (CO) climatology for the pure troposphere only, i.e. exclusively from the ground to the dynamical tropopause on an individual profile basis. The results (profiles and columns) are derived solely from the Measurements of OZone and water vapour by in-service Alrbus airCraft programme (MOZAIC) over 15 years (1994–2009). The study, focused on the northern mid-latitudes [24–50° N] and [119° W–140° E], includes more than 40 000 profiles over 11 sites to give a quasi-global zonal picture. Considering all the sites, the pure tropospheric column peak-to-peak seasonal cycle ranges are 23.7–43.2 DU for O3 and 1.7–6.9 × 10 18 molecules cm−2 for CO. The maxima of the seasonal cycles are not in phase, occurring in February–April for CO and May–July for O3. The phase shift is related to the photochemistry and OH removal efficiencies. The purely tropospheric seasonal profiles are characterized by a typical autumn–winter/spring–summer O3 dichotomy (except in Los Angeles, Eastmed – a cluster of Cairo and Tel Aviv – and the regions impacted by the summer monsoon) and a summer–autumn/winter–spring CO dichotomy. We revisit the boundary-layer, mid-tropospheric (MT) and upper-tropospheric (UT) partial columns using a~new monthly varying MT ceiling. Interestingly, the seasonal cycle maximum of the UT partial columns is shifted from summer to spring for O3 and to very early spring for CO. Conversely, the MT maximum is shifted from spring to summer and is associated with a summer (winter) MT thickening (thinning). Lastly, the pure tropospheric seasonal cycles derived from our analysis are consistent with the cycles derived from spaceborne measurements, the correlation coefficients being r=0.6–0.9 for O3 and r>0.9 for CO. The cycles observed from space are nevertheless greater than MOZAIC for O3 (by 9–18 DU) and smaller for CO (up to 1 × 10 18 molecules cm−2). The larger winter O3 difference between the two data sets suggests probable stratospheric contamination in satellite data due to the tropopause position. The study underlines the importance of rigorously discriminating between the stratospheric and tropospheric reservoirs and avoiding use of a~monthly averaged tropopause position without this strict discrimination in order to assess the pure O3 and CO tropospheric trends.

Our work is among the first that use an atmosphere-ocean general circulation model (AOGCM) with online chemistry to evaluate the impact of future aviation emissions on temperature. Other particularities of our study include non-scaling to the aviation emissions, and the analysis of models' transient response using ensemble simulations. The model we use is the Météo-France CNRM-CM5.1 earth system model extended with the REPROBUS chemistry scheme. The time horizon of our interest is 1940–2100, assuming the A1B SRES scenario. We investigate the present and future impact of aviation emissions of CO2, NOx and H2O on climate, taking into account changes in greenhouse gases, contrails and contrail-induced cirrus (CIC). As in many transport-related impact studies, we distinguish between the climate impacts of CO2 emissions and those of non-CO2 emissions. Aviation-produced aerosol is not considered in the study. Our modeling system simulated a notable sea-ice bias in the Arctic, and therefore results concerning the surface should be viewed with caution. The global averaged near-surface CO2 impact reaches around 0.1 K by the end of the 21st century, while the non-CO2 impact reaches 0.2 K in the second half of the century. The NOx emissions impact is almost negligible in our simulations, as our aviation-induced ozone production is small. As a consequence, the non-CO2 signal is very similar to the CIC signal. The seasonal analysis shows that the strongest warming due to aviation is modeled for the late summer and early autumn. In the stratosphere, a significant cooling is attributed to aviation CO2 emissions (−0.25 K by 2100). A −0.3 K temperature decrease is modeled when considering all the aviation emissions, but no significant signal appears from the CIC or NOx forcings in the stratosphere.

The behavior of the extratropical transition layer (ExTL) is investigated using a chemistry transport model (CTM) and analyses derived from assimilation of MLS (Microwave Limb Sounder) O3 and MOPITT (Measurements Of Pollution In The Troposphere) CO data. We firstly focus on a stratosphere–troposphere exchange (STE) case study that occurred on 15 August 2007 over the British Isles (50° N, 10° W). We evaluate the effect of data assimilation on the O3–CO correlations. It is shown that data assimilation disrupts the relationship in the transition region. When MLS O3 is assimilated, CO and O3 values are not consistent between each other, leading to unphysical correlations at the STE location. When MLS O3 and MOPITT CO assimilated fields are taken into account in the diagnostics the relationship happens to be more physical. We then use O3–CO correlations to quantify the effect of data assimilation on the height and depth of the ExTL. When the free-model run O3 and CO fields are used in the diagnostics, the ExTL distribution is found 1.1 km above the thermal tropopause and is 2.6 km wide (2σ). MOPITT CO analyses only slightly sharpen (by −0.02 km) and lower (by −0.2 km) the ExTL distribution. MLS O3 analyses provide an expansion (by +0.9 km) of the ExTL distribution, suggesting a more intense O3 mixing. However, the MLS O3 analyses ExTL distribution shows a maximum close to the thermal tropopause and a mean location closer to the thermal tropopause (+0.45 km). When MLS O3 and MOPITT CO analyses are used together, the ExTL shows a mean location that is the closest to the thermal tropopause (+0.16 km). We also extend the study at the global scale on 15 August 2007 and for the month of August 2007. MOPITT CO analyses still show a narrower chemical transition between stratosphere and troposphere than the free-model run. MLS O3 analyses move the ExTL toward the troposphere and broaden it. When MLS O3 analyses and MOPITT CO analyses are used together, the ExTL matches the thermal tropopause poleward of 50°.

The EU HIBISCUS project consisted of a series of field campaigns during the intense convective summers in 2001, 2003 and 2004 in the State of São Paulo in Brazil. Its objective was to investigate the impact of deep convection on the Tropical Tropopause Layer (TTL) and the lower stratosphere by providing a new set of observational data on meteorology, tracers of horizontal and vertical transport, water vapour, clouds, and chemistry in the tropical Upper Troposphere/Lower Stratosphere (UT/LS). This was achieved using short duration research balloons to study local phenomena associated with convection over land, and long-duration balloons circumnavigating the globe to study the contrast between land and oceans. Analyses of observations of short-lived tracers, ozone and ice particles show strong episodic local updraughts of cold air across the lapse rate tropopause up to 18 or 19 km (420–440 K) in the lower stratosphere by overshooting towers. The long duration balloon and satellite measurements reveal a contrast between the composition of the lower stratosphere over land and oceanic areas, suggesting significant global impact of such events. The overshoots are shown to be well captured by non-hydrostatic meso-scale Cloud Resolving Models indicating vertical velocities of 50–60 m s−1 at the top of the Neutral Buoyancy Level (NBL) at around 14 km, but, in contrast, are poorly represented by global Chemistry-Transport Models (CTM) forced by Numerical Weather Forecast Models (NWP) underestimating the overshooting process. Finally, the data collected by the HIBISCUS balloons have allowed a thorough evaluation of temperature NWP analyses and reanalyses, as well as satellite ozone, nitrogen oxide, water vapour and bromine oxide measurements in the tropics.

This paper presents an evaluation of a new linear parameterization valid for the troposphere and the stratosphere, based on a first order approximation of the carbon monoxide (CO) continuity equation. This linear scheme (hereinafter noted LINCO) has been implemented in the 3-D Chemical Transport Model (CTM) MOCAGE (MOdèle de Chimie Atmospherique Grande Echelle). First, a one and a half years of LINCO simulation has been compared to output obtained from a detailed chemical scheme output. The mean differences between both schemes are about ±25 ppbv (part per billion by volume) or 15% in the troposphere and ±10 ppbv or 100% in the stratosphere. Second, LINCO has been compared to diverse observations from satellite instruments covering the troposphere (Measurements Of Pollution In The Troposphere: MOPITT) and the stratosphere (Microwave Limb Sounder: MLS) and also from aircraft (Measurements of ozone and water vapour by Airbus in-service aircraft: MOZAIC programme) mostly flying in the upper troposphere and lower stratosphere (UTLS). In the troposphere, the LINCO seasonal variations as well as the vertical and horizontal distributions are quite close to MOPITT CO observations. However, a bias of ~−40 ppbv is observed at 700 Pa between LINCO and MOPITT. In the stratosphere, MLS and LINCO present similar large-scale patterns, except over the poles where the CO concentration is underestimated by the model. In the UTLS, LINCO presents small biases less than 2% compared to independent MOZAIC profiles. Third, we assimilated MOPITT CO using a variational 3D-FGAT (First Guess at Appropriate Time) method in conjunction with MOCAGE for a long run of one and a half years. The data assimilation greatly improves the vertical CO distribution in the troposphere from 700 to 350 hPa compared to independent MOZAIC profiles. At 146 hPa, the assimilated CO distribution is also improved compared to MLS observations by reducing the bias up to a factor of 2 in the tropics. This study confirms that the linear scheme is able to simulate reasonably well the CO distribution in the troposphere and in the lower stratosphere. Therefore, the low computing cost of the linear scheme opens new perspectives to make free runs and CO data assimilation runs at high resolution and over periods of several years.

This paper presents a comprehensive characterization of a very deep stratospheric intrusion which occurred over the British Isles on 15 August 2007. The signature of this event is diagnosed using ozonesonde measurements over Lerwick, UK (60.14° N, 1.19° W) and is also well characterized using meteorological analyses from the global operational weather prediction model of Météo-France, ARPEGE. Modelled as well as assimilated fields of both ozone (O3) and carbon monoxide (CO) have been used in order to better document this event. O3 and CO from Aura/MLS and Terra/MOPITT instruments, respectively, are assimilated into the three-dimensional chemical transport model MOCAGE of Météo-France using a variational 3-D-FGAT (First Guess at Appropriate Time) method. The validation of O3 and CO assimilated fields is done using self-consistency diagnostics and by comparison with independent observations such as MOZAIC (O3 and CO), AIRS (CO) and OMI (O3). It particularly shows in the upper troposphere and lower stratosphere region that the assimilated fields are closer to MOZAIC than the free model run. The O3 bias between MOZAIC and the analyses is −11.5 ppbv with a RMS of 22.4 ppbv and a correlation coefficient of 0.93, whereas between MOZAIC and the free model run, the corresponding values are 33 ppbv, 38.5 ppbv and 0.83, respectively. In the same way, for CO, the bias, RMS and correlation coefficient between MOZAIC and the analyses are −3.16 ppbv, 13 ppbv and 0.79, respectively, whereas between MOZAIC and the free model they are 6.3 ppbv, 16.6 ppbv and 0.71, respectively. The paper also presents a demonstration of the capability of O3 and CO assimilated fields to better describe a stratosphere-troposphere exchange (STE) event in comparison with the free run modelled O3 and CO fields. Although the assimilation of MLS data improves the distribution of O3 above the tropopause compared to the free model run, it is not sufficient to reproduce the STE event well. Assimilated MOPITT CO allows a better qualitative description of the stratospheric intrusion event. The MOPITT CO analyses appear more promising than the MLS O3 analyses in terms of their ability to capture a deep STE event. Therefore, the results of this study open the perspectives for using MOPITT CO in the STE studies.

The mechanisms of transport on annual, semi-annual and quasi-biennial time scales in the equatorial (10° S–10° N) stratosphere are investigated using the nitrous oxide (N2O) measurements of the space-borne ODIN Sub-Millimetre Radiometer from November 2001 to June 2005, and the simulations of the three-dimensional chemical transport models MOCAGE and SLIMCAT. Both models are forced with analyses from the European Centre for Medium-range Weather Forecast, but the vertical transport is derived either from the forcing analyses by solving the continuity equation (MOCAGE), or from diabatic heating rates using a radiation scheme (SLIMCAT). The N2O variations in the mid-to-upper stratosphere at levels above 32 hPa are generally well captured by the models though significant differences appear with the observations as well as between the models, attributed to the difficulty of capturing correctly the slow upwelling associated with the Brewer-Dobson circulation. However, in the lower stratosphere, below 32 hPa, the observed variations are shown to be mainly seasonal with peak amplitude at 400–450 K (~17.5–19 km), totally missed by the models. The minimum N2O in June, out of phase by two months with the known minimum seasonal upwelling associated with the Brewer-Dobson circulation and moreover amplified over the Western Pacific compared to Africa is incompatible with the seasonal change of upwelling evoked to explain the O3 annual cycle in the same altitude range (Randel et al., 2007). Unless the 1.5 ppbv amplitude of N2O annual cycle in the upper troposphere is totally wrong, the explanation of the observed N2O annual cycle of 15 ppbv in the lower stratosphere requires another mechanism. A possible candidate for that might be the existence of a downward time-averaged mass flux above specific regions, as shown by Sherwood (2000) over Indonesia, required for compensating the energy sink resulting from the deep overshooting of cold and heavy air at high altitude over intense convective areas. But, since global models do currently not capture this subsidence, it must be recognised that a full explanation of the observations cannot be provided for the moment. However, the coincidence of the peak contrast between the Western Pacific and Africa with the maximum overshooting volume in May reported by the Tropical Rainfall Measuring Mission (TRMM) Precipitation Radar, suggests a strong influence of deep convection on the chemical composition of the tropical lower stratosphere up to 500 K (21 km).

In this paper we use the total columns of nitrous oxide (N2O) as retrieved from the radiance spectra as measured by the Infrared Atmospheric Sounding Interferometer (IASI) instrument aboard the MetOp-A platform and distributed by the European Organisation for the Exploitation of Meteorological Satellites (EUMETSAT) during the March–May (MAM) 2008 period. Since the total column of N2O reflects concentrations in the middle troposphere, cloud-free columnar N2O measurements are used to assess transport processes in the equatorial band (10° S–10° N). We compare the measured data set with the outputs produced by the 3-D chemical-transport model MOCAGE during the period MAM 2002–2004. To reflect MAM 2008 concentrations, MOCAGE results have been scaled by a factor 1.0125 in order to represent the change in concentration of N2O since 2004. IASI N2O equatorial measurements show a maximum over Africa (4.96×10−3 kg m−2) and a minimum over South America (4.86×10−3 kg m−2) in reasonable agreement with the outputs from MOCAGE despite the fact that emissions of N2O are more intense over America than over Africa. The amplitude of the longitudinal variation of total column N2O along the equatorial band is twice as intense in the measurements (~1.6%) than as in the model calculations (~0.8%), and much greater than the IASI mean random error (0.16–0.33%). A difference between the two data sets is observed above the Western Pacific (110° E–150° E) with a marked minimum in IASI compared to MOCAGE. Recent theoretical studies (Ricaud et al., 2007 and 2009) have shown the potentially important effect of the Walker and the Hadley cells on the tropospheric distribution of N2O in producing a local maximum in N2O above Africa. Based on equatorial total columns of N2O retrieved from IASI, our results are consistent with the fact that Africa is a zone of convergence of airmasses coming from different convective regions whilst Western Pacific behaves more like a divergence zone.

Simulations of CO, N2O and CH4 from a coupled chemistry-climate model (CMAM) are compared with satellite measurements from Odin Sub-Millimeter Radiometer (Odin/SMR), Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and Aura Microwave Limb Sounder (Aura/MLS). Pressure-latitude cross-sections and seasonal time series demonstrate that CMAM reproduces the observed global CO, N2O, and CH4 distributions quite well. Generally, excellent agreement with measurements is found between CO simulations and observations in the stratosphere and mesosphere. Differences between the simulations and the ACE-FTS observations are generally within 30%, and the differences between CMAM results and SMR and MLS observations are slightly larger. These differences are comparable with the difference between the instruments in the upper stratosphere and mesosphere. Comparisons of N2O show that CMAM results are usually within 15% of the measurements in the lower and middle stratosphere, and the observations are close to each other. However, the standard version of CMAM has a low N2O bias in the upper stratosphere. The CMAM CH4 distribution also reproduces the observations in the lower stratosphere, but has a similar but smaller negative bias in the upper stratosphere. The negative bias may be due to that the gravity drag is not fully resolved in the model. The simulated polar CO evolution in the Arctic and Antarctic agrees with the ACE and MLS observations. CO measurements from 2006 show evidence of enhanced descent of air from the mesosphere into the stratosphere in the Arctic after strong stratospheric sudden warmings (SSWs). CMAM also shows strong descent of air after SSWs. In the tropics, CMAM captures the annual oscillation in the lower stratosphere and the semiannual oscillations at the stratopause and mesopause seen in Aura/MLS CO and N2O observations and in Odin/SMR N2O observations. The Odin/SMR and Aura/MLS N2O observations also show a quasi-biennial oscillation (QBO) in the upper stratosphere, whereas, the CMAM does not have QBO included. This study confirms that CMAM is able to simulate middle atmospheric transport processes reasonably well.

The Odin satellite carries two instruments capable of determining stratospheric ozone profiles by limb sounding: the Sub-Millimetre Radiometer (SMR) and the UV-visible spectrograph of the OSIRIS (Optical Spectrograph and InfraRed Imager System) instrument. A large number of ozone profiles measurements were performed during six years from November 2001 to present. This ozone dataset is here used to make quantitative comparisons with satellite measurements in order to assess the quality of the Odin/SMR ozone measurements. In a first step, we compare Swedish SMR retrievals version 2.1, French SMR ozone retrievals version 222 (both from the 501.8 GHz band), and the OSIRIS retrievals version 3.0, with the operational version 4.0 ozone product from POAM III (Polar Ozone Atmospheric Measurement). In a second step, we refine the Odin/SMR validation by comparisons with ground-based instruments and balloon-borne observations. We use observations carried out within the framework of the Network for Detection of Atmospheric Composition Change (NDACC) and balloon flight missions conducted by the Canadian Space Agency (CSA), the Laboratoire de Physique et de Chimie de l'{}Environnement (LPCE, Orléans, France), and the Service d'Aéronomie (SA, Paris, France). Coincidence criteria were 5° in latitude×10° in longitude, and 5 h in time in Odin/POAM III comparisons, 12 h in Odin/NDACC comparisons, and 72 h in Odin/balloons comparisons. An agreement is found with the POAM III experiment (10–60 km) within −0.3±0.2 ppmv (bias±standard deviation) for SMR (v222, v2.1) and within −0.5±0.2 ppmv for OSIRIS (v3.0). Odin ozone mixing ratio products are systematically slightly lower than the POAM III data and show an ozone maximum lower by 1–5 km in altitude. The comparisons with the NDACC data (10–34 km for ozonesonde, 10–50 km for lidar, 10–60 for microwave instruments) yield a good agreement within −0.15±0.3 ppmv for the SMR data and −0.3±0.3 ppmv for the OSIRIS data. Finally the comparisons with instruments on large balloons (10–31 km) show a good agreement, within −0.7±1 ppmv. The official SMR v2.1 dataset is consistent in all altitude ranges with POAM III, NDACC and large balloon-borne instruments measurements. In the SMR v2.1 data, no different systematic error has been found in the 0–35km range in comparison with the 35–60 km range. The same feature has been highlighted in both hemispheres in SMR v2.1/POAM III intercomparisons, and no latitudinal dependence has been revealed in SMR v2.1/NDACC intercomparisons.

The transport pathways of carbon monoxide (CO) in the African Upper Troposphere (UT) during the West African Monsoon (WAM) is investigated through the assimilation of CO observations by the Aura Microwave Limb Sounder (MLS) in the MOCAGE Chemistry Transport Model (CTM). The assimilation setup, based on a 3-D First Guess at Assimilation Time (3-D-FGAT) variational method is described. Comparisons between the assimilated CO fields and in situ airborne observations from the MOZAIC program between Europe and both Southern Africa and Southeast Asia show an overall good agreement around the lowermost pressure level sampled by MLS (~215 hPa). The 4-D assimilated fields averaged over the month of July 2006 have been used to determine the main dynamical processes responsible for the transport of CO in the African UT. The studied period corresponds to the second AMMA (African Monsoon Multidisciplinary Analyses) aircraft campaign. At 220 hPa, the CO distribution is characterized by a latitudinal maximum around 5° N mostly driven by convective uplift of air masses impacted by biomass burning from Southern Africa, uplifted within the WAM region and vented predominantly southward by the upper branch of the winter hemisphere Hadley cell. Above 150 hPa, the African CO distribution is characterized by a broad maximum over northern Africa. This maximum is mostly controlled by the large scale UT circulation driven by the Asian Summer Monsoon (ASM) and characterized by the Asian Monsoon Anticyclone (AMA) centered at 30° N and the Tropical Easterly Jet (TEJ) on the southern flank of the anticyclone. Asian pollution uplifted to the UT over large region of Southeast Asia is trapped within the AMA and transported by the anticyclonic circulation over Northeast Africa. South of the AMA, the TEJ is responsible for the tranport of CO-enriched air masses from India and Southeast Asia over Africa. Using the high time resolution provided by the 4-D assimilated fields, we give evidence that the variability of the African CO distribution above 150 hPa and north of the WAM region is mainly driven by the synoptic dynamical variability of both the AMA and the TEJ.

The Atmospheric Chemistry Experiment (ACE) mission was launched in August 2003 to sound the atmosphere by solar occultation. Carbon monoxide (CO), a good tracer of pollution plumes and atmospheric dynamics, is one of the key species provided by the primary instrument, the ACE-Fourier Transform Spectrometer (ACE-FTS). This instrument performs measurements in both the CO 1-0 and 2-0 ro-vibrational bands, from which vertically resolved CO concentration profiles are retrieved, from the mid-troposphere to the thermosphere. This paper presents an updated description of the ACE-FTS version 2.2 CO data product, along with a comprehensive validation of these profiles using available observations (February 2004 to December 2006). We have compared the CO partial columns with ground-based measurements using Fourier transform infrared spectroscopy and millimeter wave radiometry, and the volume mixing ratio profiles with airborne (both high-altitude balloon flight and airplane) observations. CO satellite observations provided by nadir-looking instruments (MOPITT and TES) as well as limb-viewing remote sensors (MIPAS, SMR and MLS) were also compared with the ACE-FTS CO products. We show that the ACE-FTS measurements provide CO profiles with small retrieval errors (better than 5% from the upper troposphere to 40 km, and better than 10% above). These observations agree well with the correlative measurements, considering the rather loose coincidence criteria in some cases. Based on the validation exercise we assess the following uncertainties to the ACE-FTS measurement data: better than 15% in the upper troposphere (8–12 km), than 30% in the lower stratosphere (12–30 km), and than 25% from 30 to 100 km.

The mechanism of troposphere-stratosphere exchange in the tropics was investigated from space-borne observations of the horizontal distributions of tropospheric-origin long-lived species, nitrous oxide (N2O), methane (CH4) and carbon monoxide (CO), from 150 to 70 hPa in March-April-May by the ODIN/Sub-Millimeter Radiometer (SMR), the Upper Atmosphere Research Satellite (UARS)/Halogen Occultation Experiment (HALOE) and the TERRA/Measurements Of Pollution In The Troposphere (MOPITT) instruments in 2002–2004, completed by recent observations of the AURA/Microwave Limb Sounder (MLS) instrument during the same season in 2005. The vertical resolution of the satellite measurements ranges from 2 to 4 km. The analysis has been performed on isentropic surfaces: 400 K (lower stratosphere) for all the species and 360 K (upper troposphere) only for CO. At 400 K (and 360 K for CO), all gases show significant longitudinal variations with peak-to-trough values of ~5–11 ppbv for N2O, 0.07–0.13 ppmv for CH4, and ~10 ppbv for CO (~40 ppbv at 360 K). The maximum amounts are primarily located over Africa and, depending on the species, secondary more or less pronounced maxima are reported above northern South America and South-East Asia. The lower stratosphere over the Western Pacific deep convective region where the outgoing longwave radiation is the lowest, the tropopause the highest and the coldest, appears as a region of minimum concentration of tropospheric trace species. The possible impact on trace gas concentration at the tropopause of the inhomogeneous distribution and intensity of the sources, mostly continental, of the horizontal and vertical transports in the troposphere, and of cross-tropopause transport was explored with the MOCAGE Chemistry Transport Model. In the simulations, significant longitudinal variations were found on the medium-lived CO (2-month lifetime) with peak-to-trough value of ~20 ppbv at 360 K and ~10 ppbv at 400 K, slightly weaker than observations. However, the CH4 (8–10 year lifetime) and N2O (130-year lifetime) longitudinal variations are significantly weaker than observed: peak-to-trough values of ~0.02 ppmv for CH4 and 1–2 ppbv for N2O at 400 K. The large longitudinal contrast of N2O and CH4 concentrations reported by the space-borne instruments at the tropopause and in the lower stratosphere not captured by the model thus requires another explanation. The suggestion is of strong overshooting over land convective regions, particularly Africa, very consistent with the space-borne Tropical Rainfall Measuring Mission (TRMM) radar maximum overshooting features over the same region during the same season. Compared to observations, the MOCAGE model forced by ECMWF analyses is found to ignore these fast local uplifts, but to overestimate the average uniform vertical transport in the UTLS at all longitudes in the tropics.

We present the configuration of the Météo-France Chemistry and Transport Model (CTM) MOCAGE-Climat that will be dedicated to the study of chemistry and climate interactions. MOCAGE-Climat is a state-of-the-art CTM that simulates the global distribution of ozone and its precursors (82 chemical species) both in the troposphere and the stratosphere, up to the mid-mesosphere (~70 km). Surface processes (emissions, dry deposition), convection, and scavenging are explicitly described in the model that has been driven by the ECMWF operational analyses of the period 2000–2005, on T21 and T42 horizontal grids and 60 hybrid vertical levels, with and without a procedure that reduces calculations in the boundary layer, and with on-line or climatological deposition velocities. Model outputs have been compared to available observations, both from satellites (TOMS, HALOE, SMR, SCIAMACHY, MOPITT) and in-situ instrument measurements (ozone sondes, MOZAIC and aircraft campaigns) at climatological timescales. The distribution of long-lived species is in fair agreement with observations in the stratosphere putting aside the shortcomings associated with the large-scale circulation. The variability of the ozone column, both spatially and temporarily, is satisfactory. However, because the Brewer-Dobson circulation is too fast, too much ozone is accumulated in the lower to mid-stratosphere at the end of winter. Ozone in the UTLS region does not show any systematic bias. In the troposphere better agreement with ozone sonde measurements is obtained at mid and high latitudes than in the tropics and differences with observations are the lowest in summer. Simulations using a simplified boundary layer lead to larger ozone differences between the model and the observations up to the mid-troposphere. NOx in the lowest troposphere is in general overestimated, especially in the winter months over the Northern Hemisphere, which may result from a positive bias in OH. Dry deposition fluxes of O3 and nitrogen species are within the range of values reported by recent inter-comparison model exercises. The use of climatological deposition velocities versus deposition velocities calculated on-line had greatest impact on HNO3 and NO2 in the troposphere.

We have used an off-line three-dimensional (3-D) chemical transport model (CTM) to study long-term changes in stratospheric O3. The model was run from 1977–2004 and forced by ECMWF ERA-40 and operational analyses. Model runs were performed to examine the impact of increasing halogens and additional stratospheric bromine from short-lived source gases. The analyses capture much of the observed interannual variability in column ozone, but there are also unrealistic features. In particular the ERA-40 analyses cause a large positive anomaly in northern hemisphere (NH) column O3 in the late 1980s. Also, the change from ERA-40 to operational winds at the start of 2002 introduces abrupt changes in some model fields (e.g. temperature, ozone) which affect analysis of trends. The model reproduces the observed column increase in NH mid-latitudes from the mid 1990s. Analysis of a run with fixed halogens shows that this increase is not due to a significant decrease in halogen-induced loss, i.e. is not an indication of recovery. The model predicts only a small decrease in halogen-induced loss after 1999. In the upper stratosphere, despite the modelled turnover of chlorine around 1999, O3 does not increase because of the effects of increasing ECMWF temperatures, decreasing modelled CH4 at this altitude, and abrupt changes in the SH temperatures at the end of the ERA-40 period. The impact of an additional 5 pptv stratospheric bromine from short-lived species decreases mid-latitude column O3 by about 10 DU. However, the impact on the modelled relative O3 anomaly is generally small except during periods of large volcanic loading.