on ozone loss in the middle atmosphere during very large solar proton events Monali Borthakur1, Miriam Sinnhuber1, Alexandra Laeng1, Thomas Reddmann1, Peter Braesicke1, Gabriele Stiller1, Thomas von Clarmann1, Bernd Funke2, Ilya Usoskin3, Jan Maik Wissing4, and Olesya Yakovchuk4 1Institute of Meteorology and Climate research, Karlsruhe Institute of Technology, Karlsruhe, Germany 2Instituto de Astrofísica de Andalucía, CSIC, Granada, Spain 3University of Oulu, Oulu, Finland 4University of Rostock, Rostock, Germany

Precipitating auroral and radiation belt electrons are considered an important part of the natural forcing of the climate system. Recent studies suggest that this forcing is underestimated in current chemistry‐climate models. The High Energy Particle Precipitation in the Atmosphere III intercomparison experiment is a collective effort to address this point. Here, eight different estimates of medium energy electron (MEE) (>30keV) $(> 30\hspace*{.5em}keV)$ ionization rates are assessed during a geomagnetic active period in April 2010. The objective is to understand the potential uncertainty related to the MEE energy input. The ionization rates are all based on the Medium Energy Proton and Electron Detector (MEPED) on board the NOAA/POES and EUMETSAT/MetOp spacecraft series. However, different data handling, ionization rate calculations, and background atmospheres result in a wide range of mesospheric electron ionization rates. Although the eight data sets agree well in terms of the temporal variability, they differ by about an order of magnitude in ionization rate strength both during geomagnetic quiet and disturbed periods. The largest spread is found in the aftermath of enhanced geomagnetic activity. Furthermore, governed by different energy limits, the atmospheric penetration depth varies, and some differences related to latitudinal coverage are also evident. The mesospheric NO densities simulated with the Whole Atmospheric Community Climate Model driven by highest and lowest ionization rates differ by more than a factor of eight. In a follow‐up study, the atmospheric responses are simulated in four chemistry‐climate models (CCM) and compared to satellite observations, considering both the CCM structure and the ionization forcing.

Precipitating auroral and radiation belt electrons are considered to play an important part in the natural forcing of the middle atmosphere with a possible impact on the climate system. Recent studies suggest that this forcing is underestimated in current chemistry‐climate models. The HEPPA III intercomparison experiment is a collective effort to address this point.

Sudden stratospheric warming (SSW) is a unique atmospheric phenomenon, which consists in a rapid rise of temperature at altitudes of ~30–40 km in high latitudes of the winter, typically, northern hemisphere. Modeling SSW effects in the mesosphere, thermosphere, and ionosphere is a challenging problem, because it must be done on a global scale, with consideration of numerous physical and chemical processes. This paper reports the results of calculations of the characteristics of total electron content (TEC) perturbations for the conditions of the SSW event in January 2009. The calculations are performed using the Global Self-Consistent Model of the Thermosphere, Ionosphere and Protonosphere (GSM TIP) supplemented by the lower boundary conditions in the form of space–time distributions of the basic parameters of the mesosphere at an altitude of 80 km, as calculated by the SOCOL, KASIMA, and TIME GCM models. The simulation results show that, for some versions, the spatial distribution of total electron content disturbances ΔTEC shows a qualitative agreement with experimental data; however, the values of ΔTEC in all variants of calculations proved to be an order of magnitude lower than the measured.

A new and improved setup of the SF6 retrieval together with a newly calibrated version of MIPAS-ENVISAT level 1b spectra (version 5, ESA data version 5.02/5.06) was used to obtain a new global SF6 data set, covering the total observational period of MIPAS from July 2002 to April 2012 for the first time. Monthly and zonally averaged SF6 profiles were converted into mean age of air using a tropospheric SF6-reference curve. The obtained data set of age of air was compared to airborne age of air measurements. The temporal evolution of the mean age of air was then investigated in 10° latitude and 1–2 km altitude bins. A regression model consisting of a constant and a linear trend term, two proxies for the quasi-biennial oscillation variation, sinusoidal terms for the seasonal and semiannual variation and overtones was fitted to the age of air time series. The annual cycle for particular regions in the stratosphere was investigated and compared to other studies. The age of air trend over the total MIPAS period consisting of the linear term was assessed and compared to previous findings of Stiller et al. (2012). While the linear increase of mean age is confirmed to be positive for the northern midlatitudes and southern polar middle stratosphere, differences are found in the northern polar upper stratosphere, where the mean age is now found to increase as well. The magnitude of trends in the northern midlatitude middle stratosphere is slightly lower compared to the previous version and the trends fit remarkably well to the trend derived by Engel et al. (2009). Negative age of air trends found by Stiller et al. (2012) are confirmed for the lowermost tropical stratosphere and lowermost southern midlatitudinal stratosphere. Differences to the previous data versions occur in the middle tropical stratosphere around 25 km, where the trends are now negative. Overall, the new latitude–altitude distribution of trends appears to be less patchy and more coherent than the previous one. The new data provide evidence of an accelerating shallow branch of the Brewer–Dobson circulation, at least in the Southern Hemisphere. Finally the age of air decadal trends are compared to trends calculated with simulated SF6 values by the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA) and good agreement is found. The hemispheric asymmetry in the trends found in the MIPAS data is also indicated in the trends calculated with simulated SF6 values by the KASIMA model.

Policies have been in place since 1987 to reduce the release of chlorine atoms in the stratosphere, where they deplete ozone; here observations show that since 2007 hydrogen chloride has been increasing in the lower stratosphere of the Northern Hemisphere, an increase that is attributed to a slowdown in atmospheric circulation. The Montreal Protocol, the 1987 UN treaty that restricted the use of the major chlorine- and bromine-containing halocarbons that were damaging the stratospheric ozone layer, has led to a decrease in the main stratospheric chlorine reservoir, hydrogen chloride. This paper reports a recent increase in hydrogen chloride in the Northern Hemisphere. With the help of a model study, the authors attribute the phenomenon to a short-term slowdown in the Northern Hemisphere atmospheric circulation that transports aged air, with a larger relative conversion of chlorine source gases to hydrogen chloride in the lower stratosphere. The increase in hydrogen chloride is not the result of unaccounted emissions from chlorine-containing source gases and the Montreal treaty continues to lead to an overall long-term reduction in stratospheric halogens. The abundance of chlorine in the Earth’s atmosphere increased considerably during the 1970s to 1990s, following large emissions of anthropogenic long-lived chlorine-containing source gases, notably the chlorofluorocarbons. The chemical inertness of chlorofluorocarbons allows their transport and mixing throughout the troposphere on a global scale1, before they reach the stratosphere where they release chlorine atoms that cause ozone depletion2. The large ozone loss over Antarctica3 was the key observation that stimulated the definition and signing in 1987 of the Montreal Protocol, an international treaty establishing a schedule to reduce the production of the major chlorine- and bromine-containing halocarbons. Owing to its implementation, the near-surface total chlorine concentration showed a maximum in 1993, followed by a decrease of half a per cent to one per cent per year4, in line with expectations. Remote-sensing data have revealed a peak in stratospheric chlorine after 19965, then a decrease of close to one per cent per year6,7, in agreement with the surface observations of the chlorine source gases and model calculations7. Here we present ground-based and satellite data that show a recent and significant increase, at the 2σ level, in hydrogen chloride (HCl), the main stratospheric chlorine reservoir, starting around 2007 in the lower stratosphere of the Northern Hemisphere, in contrast with the ongoing monotonic decrease of near-surface source gases. Using model simulations, we attribute this trend anomaly to a slowdown in the Northern Hemisphere atmospheric circulation, occurring over several consecutive years, transporting more aged air to the lower stratosphere, and characterized by a larger relative conversion of source gases to HCl. This short-term dynamical variability will also affect other stratospheric tracers and needs to be accounted for when studying the evolution of the stratospheric ozone layer.

MIPAS-ENVISAT full resolution spectra were analyzed to obtain a global distribution of hydrogen peroxide (H2O2) in the stratosphere. H2O2 acts as reservoir gas for the HOx family (= H+OH+HO2) and thus, observations of H2O2 provide a better understanding of the HOx chemistry in the atmosphere. A retrieval approach based on constrained least squares fitting was developed and applied to small dedicated spectral analysis windows with maximum H2O2 information and minimum contribution of interfering gases. Due to a low signal to noise ratio in the measured spectra single profiles cannot be used for scientific interpretation and about 100 profiles have to be averaged temporally or spatially. Our retrievals of H2O2 from MIPAS measurements provide meaningful results between approximately 20 and 60 km. A possible impact by the high uncertainty of the reaction rate constant for HO2 + HO2→H2O2 + O2 in our 3D-CTM KASIMA is discussed. We find best agreement between model and observations for applying rate constants according to Christensen et al. (2002) however, a mismatch in vertical profile shape remains. The observations were compared to the model results of KASIMA focusing on low to mid latitudes. Good agreement in spatial distribution and in temporal evolution was found. Highest vmr of H2O2 in the stratosphere were observed and modeled in low latitudes shortly after equinox at about 30 km. The modelled diurnal cycle with lowest vmr shortly after sunrise and highest vmr in the afternoon is confirmed by the MIPAS observations.

We have compared composition changes of NO, NO2, H2O2, O3, N2O, HNO3, N2O5, HNO4, ClO, HOCl, and ClONO2 as observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat in the aftermath of the "Halloween" solar proton event (SPE) in late October 2003 at 25–0.01 hPa in the Northern Hemisphere (40–90° N) and simulations performed by the following atmospheric models: the Bremen 2-D model (B2dM) and Bremen 3-D Chemical Transport Model (B3dCTM), the Central Aerological Observatory (CAO) model, FinROSE, the Hamburg Model of the Neutral and Ionized Atmosphere (HAMMONIA), the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA), the ECHAM5/MESSy Atmospheric Chemistry (EMAC) model, the modeling tool for SOlar Climate Ozone Links studies (SOCOL and SOCOLi), and the Whole Atmosphere Community Climate Model (WACCM4). The large number of participating models allowed for an evaluation of the overall ability of atmospheric models to reproduce observed atmospheric perturbations generated by SPEs, particularly with respect to NOy and ozone changes. We have further assessed the meteorological conditions and their implications for the chemical response to the SPE in both the models and observations by comparing temperature and tracer (CH4 and CO) fields.Simulated SPE-induced ozone losses agree on average within 5 % with the observations. Simulated NOy enhancements around 1 hPa, however, are typically 30 % higher than indicated by the observations which are likely to be related to deficiencies in the used ionization rates, though other error sources related to the models' atmospheric background state and/or transport schemes cannot be excluded. The analysis of the observed and modeled NOy partitioning in the aftermath of the SPE has demonstrated the need to implement additional ion chemistry (HNO3 formation via ion-ion recombination and water cluster ions) into the chemical schemes. An overestimation of observed H2O2 enhancements by all models hints at an underestimation of the OH/HO2 ratio in the upper polar stratosphere during the SPE. The analysis of chlorine species perturbations has shown that the encountered differences between models and observations, particularly the underestimation of observed ClONO2 enhancements, are related to a smaller availability of ClO in the polar night region already before the SPE. In general, the intercomparison has demonstrated that differences in the meteorology and/or initial state of the atmosphere in the simulations cause a relevant variability of the model results, even on a short timescale of only a few days.

The tropical transport processes of 14 different models or model versions were compared, within the framework of the SCOUT-O3 (Stratospheric-Climate Links with Emphasis on the Upper Troposphere and Lower Stratosphere) project. The tested models range from the regional to the global scale, and include numerical weather prediction (NWP), chemical transport, and chemistry-climate models. Idealised tracers were used in order to prevent the model's chemistry schemes from influencing the results substantially, so that the effects of modelled transport could be isolated. We find large differences in the vertical transport of very short-lived tracers (with a lifetime of 6 h) within the tropical troposphere. Peak convective outflow altitudes range from around 300 hPa to almost 100 hPa among the different models, and the upper tropospheric tracer mixing ratios differ by up to an order of magnitude. The timing of convective events is found to be different between the models, even among those which source their forcing data from the same NWP model (ECMWF). The differences are less pronounced for longer lived tracers, however they could have implications for modelling the halogen burden of the lowermost stratosphere through transport of species such as bromoform, or short-lived hydrocarbons into the lowermost stratosphere. The modelled tracer profiles are strongly influenced by the convective transport parameterisations, and different boundary layer mixing parameterisations also have a large impact on the modelled tracer profiles. Preferential locations for rapid transport from the surface into the upper troposphere are similar in all models, and are mostly concentrated over the western Pacific, the Maritime Continent and the Indian Ocean. In contrast, models do not indicate that upward transport is highest over western Africa.

Energetic particle precipitation during solar active periods induces enhancements of NOx (N, NO, NO2) in the lower thermosphere/mesosphere which can be transported to the stratosphere within the polar vortex. The quantitative contribution of these NOx intrusions to ozone chemistry in the stratosphere is still under discussion. Here we present simulations with a three‐dimensional model of the middle atmosphere where NOx enhancements in the lower mesosphere have been taken from the observations of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument on the European Space Agency satellite ENVISAT. Covering the period from July 2002 to March 2004 these observations include the strong solar proton event in fall 2003 and intrusions connected to auroral events during the Arctic and Antarctic winters. The comparison of the disturbed run with the undisturbed model run allows a quantitative assessment of the long‐term influence of NOx intrusions on stratospheric chemistry in general and the ozone concentration in particular. From the model simulation, we estimate for the period from July 2002 to March 2004 that in total, an additional 5.4 Gigamol NOy has been brought into the middle atmosphere. This represents in early 2004 about 5% of the global NOy mass in the middle atmosphere. A 2 year decay time for such enhancements is estimated from the model. Persistent reduction of ozone concentration in the stratosphere caused by the NOx intrusions can be followed in the simulation for several months. This reduction is restricted to high latitudes and amounts to several Dobson units in the total ozone column.

Abstract. The tropical transport processes of 14 different models or model versions were compared, within the framework of the SCOUT-O3 (Stratospheric-Climate Links with Emphasis on the Upper Troposphere and Lower Stratosphere) project. The tested models range from the regional to the global scale, and include numerical weather prediction (NWP), chemistry transport, and climate chemistry models. Idealised tracers were used in order to prevent the model's chemistry schemes from influencing the results substantially, so that the effects of modelled transport could be isolated. We find large differences in the vertical transport of very short lived tracers (with a lifetime of 6 hours) within the tropical troposphere. Peak convective outflow altitudes range from around 300 hPa to almost 100 hPa among the different models, and the upper tropospheric tracer mixing ratios differ by up to an order of magnitude. The timing of convective events is found to differ between the models, even among those which source their forcing data from the same NWP model (ECMWF). The differences are less pronounced for longer lived tracers, however they could have implications for the modelling of the halogen burden of the lowermost stratosphere through species such as bromoform, or for the transport of short lived hydrocarbons into the lowermost stratosphere. The modelled tracer profiles are found to be strongly influenced by the convective transport parameterisations, and boundary layer mixing parameterisations of the models. The location of rapid transport into the upper troposphere is similar among the models, and is mostly concentrated over the western Pacific, the Maritime Continent and the Indian Ocean. In contrast, none of the models indicates significant enhancement in upward transport over western Africa. The mean mixing ratios of an idealised CO like tracer in the upper tropical troposphere are found to be sensitive to the surface CO mixing ratios in the regions with the most active convection, revealing the importance of correctly modelling both the location of convective transport and the geographical pollutant emission patterns.

In the 2002 Antarctic polar vortex enhanced HOCl mixing ratios were detected by the Michelson Interferometer for Passive Atmospheric Sounding both at altitudes of around 35 km (1000 K potential temperature), where HOCl abundances are ruled by gas phase chemistry and at around 18–24 km (475–625 K), which belongs to the altitude domain where heterogeneous chlorine chemistry is relevant. At altitudes of 33 to 40 km polar vortex HOCl mixing ratios were found to be around 0.14 ppbv as long as the polar vortex was intact, centered at the pole, and thus received relatively little sunlight. This is the altitude region where in midlatitudinal and tropic atmospheres peak HOCl mixing ratios significantly above 0.2 ppbv (in terms of daily mean values) are observed. After deformation and displacement of the polar vortex in the course of a major warming, ClO-rich vortex air was more exposed to sunlight, where enhanced HOx abundances led to largely increased HOCl mixing ratios (up to 0.3 ppbv), exceeding typical midlatitudinal and tropical amounts significantly. The HOCl increase was preceded by an increase of ClO. Model runs could reproduce these measurements only when the Stimpfle et al. (1979) rate constant for the reaction ClO+HO2→HOCl+O2 was used but not with the current JPL recommendation. At an altitude of 24 km, HOCl mixing ratios of up to 0.15 ppbv were detected. This HOCl enhancement, which is already visible in 18 September data, is attributed to heterogeneous chemistry, which is in agreement with observations of polar stratospheric clouds. The measurements were compared to a model run where no polar stratospheric clouds appeared during the observation period. The fact that HOCl still was produced in the model run suggests that a significant part of HOCl was generated from ClO rather than directly via heterogeneous reaction. Excess ClO, lower ClONO2 and earlier loss of HOCl in the measurements are attributed to ongoing heterogeneous chemistry which is not reproduced by the model. On 11 October, polar vortex mean daytime mixing ratios were only 0.03 ppbv.

Global distributions of profiles of sulphur hexafluoride (SF6) have been retrieved from limb emission spectra recorded by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat covering the period September 2002 to March 2004. Individual SF6 profiles have a precision of 0.5 pptv below 25 km altitude and a vertical resolution of 4–6 km up to 35 km altitude. These data have been validated versus in situ observations obtained during balloon flights of a cryogenic whole-air sampler. For the tropical troposphere a trend of 0.230±0.008 pptv/yr has been derived from the MIPAS data, which is in excellent agreement with the trend from ground-based flask and in situ measurements from the National Oceanic and Atmospheric Administration Earth System Research Laboratory, Global Monitoring Division. For the data set currently available, based on at least three days of data per month, monthly 5° latitude mean values have a 1σ standard error of 1%. From the global SF6 distributions, global daily and monthly distributions of the apparent mean age of air are inferred by application of the tropical tropospheric trend derived from MIPAS data. The inferred mean ages are provided for the full globe up to 90° N/S, and have a 1σ standard error of 0.25 yr. They range between 0 (near the tropical tropopause) and 7 years (except for situations of mesospheric intrusions) and agree well with earlier observations. The seasonal variation of the mean age of stratospheric air indicates episodes of severe intrusion of mesospheric air during each Northern and Southern polar winter observed, long-lasting remnants of old, subsided polar winter air over the spring and summer poles, and a rather short period of mixing with midlatitude air and/or upward transport during fall in October/November (NH) and April/May (SH), respectively, with small latitudinal gradients, immediately before the new polar vortex starts to form. The mean age distributions further confirm that SF6 is destroyed in the mesosphere to a considerable degree. Model calculations with the Karlsruhe simulation model of the middle atmosphere (KASIMA) chemical transport model agree well with observed global distributions of the mean age only if the SF6 sink reactions in the mesosphere are included in the model.

Satellite observations show that the enormous solar proton events (SPEs) in October–November 2003 had significant effects on the composition of the stratosphere and mesosphere in the polar regions. After the October–November 2003 SPEs and in early 2004, significant enhancements of NOx(=NO+NO2) in the upper stratosphere and lower mesosphere in the Northern Hemisphere were observed by several satellite instruments. Here we present global full chemistry calculations performed with the CLaMS model to study the impact of mesospheric NOx intrusions on Arctic polar ozone loss processes in the stratosphere. Several model simulations are preformed with different upper boundary conditions for NOx at 2000 K potential temperature (≈50 km altitude). In our study we focus on the impact of the non-local production of NOx, which means the downward transport of enhanced NOx from the mesosphere to the stratosphere. The local production of NOx in the stratosphere is neglected. Our findings show that intrusions of mesospheric air into the stratosphere, transporting high burdens of NOx, affect the composition of the Arctic polar region down to about 400 K (≈17–18 km). We compare our simulated NOx and O3 mixing ratios with satellite observations by ACE-FTS and MIPAS processed at IMK/IAA and derive an upper limit for the ozone loss caused by enhanced mesospheric NOx. Our findings show that in the Arctic polar vortex (equivalent lat.>70° N) the accumulated column ozone loss between 350–2000 K potential temperature (≈14–50 km altitude) caused by the SPEs in October–November 2003 in the stratosphere is up to 3.3 DU with an upper limit of 5.5 DU until end of November. Further, we found that about 10 DU, but in any case lower than 18 DU, accumulated ozone loss additionally occurred until end of March 2004 caused by the transport of mesospheric NOx-rich air in early 2004. The solar-proton-produced NOx above 55 km due to the SPEs of October–November 2003 had a negligibly small impact on ozone loss processes through the end of November in the lower stratosphere (350–700 K≈14–27 km). The mesospheric NOx intrusions in early 2004 yielded a lower stratospheric ozone loss of about 3.5 DU, and clearly lower than 6.5 DU through the end of March. Overall, the non-local production of NOx is an additional variability in the existing variations of the ozone loss observed in the Arctic.