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Observational monitoring of the stratospheric transport circulation, the Brewer–Dobson circulation (BDC), is crucial to estimate any decadal to long-term changes therein, a prerequisite to interpret trends in stratospheric composition and to constrain the consequential impacts on climate. The transport time along the BDC (i.e. the mean stratospheric age of air, AoA) can best be deduced from trace gas measurements of tracers which increase linearly with time and are chemically passive. The gas sulfur hexafluoride (SF6) is often used to deduce AoA because it has been increasing monotonically since the ∼1950s, and previously its chemical sinks in the mesosphere have been assumed to be negligible for AoA estimates. However, recent studies have shown that the chemical sinks of SF6 are stronger than assumed and become increasingly relevant with rising SF6 concentrations. To adjust biases in AoA that result from the chemical SF6 sinks, we here propose a simple correction scheme for SF6-based AoA estimates accounting for the time-dependent effects of chemical sinks. The correction scheme is based on theoretical considerations with idealized assumptions, resulting in a relation between ideal AoA and apparent AoA which is a function of the tropospheric reference time series of SF6 and of the AoA-dependent effective lifetime of SF6. The correction method is thoroughly tested within a self-consistent data set from a climate model that includes explicit calculation of chemical SF6 sinks. It is shown within the model that the correction successfully reduces biases in SF6-based AoA to less than 5 % for mean ages below 5 years. Tests using only subsampled data for deriving the fit coefficients show that applying the correction scheme even with imperfect knowledge of the sink is far superior to not applying a sink correction. Furthermore, we show that based on currently available measurements, we are not able to constrain the fit parameters of the correction scheme based on observational data alone. However, the model-based correction curve lies within the observational uncertainty, and we thus recommend using the model-derived fit coefficients until more high-quality measurements are able to further constrain the correction scheme. The application of the correction scheme to AoA from satellites and in situ data suggests that it is highly beneficial to reconcile different observational estimates of mean AoA.

Stratospheric ozone is important for both stratospheric and surface climate. In the lower stratosphere during winter, its variability is governed primarily by transport dynamics induced by wave–mean flow interactions. In this work, we analyze interannual co-variations between the distribution of zonal-mean ozone and the strength of the polar vortex as a measure of dynamical activity during northern hemispheric winter. Specifically, we study co-variability between the seasonal means of the ozone field from modern reanalyses and polar-cap-averaged temperature at 100 hPa, which represents a robust and well-defined index for polar vortex strength. We focus on the vertically resolved structure of the associated extratropical ozone anomalies relative to the winter climatology and shed light on the transport mechanisms that are responsible for this response pattern. In particular, regression analysis in pressure coordinates shows that anomalously weak polar vortex years are associated with three pronounced local ozone maxima just above the polar tropopause, in the lower to mid-stratosphere and near the stratopause. In contrast, in isentropic coordinates, using ERA-Interim reanalysis data, only the mid- to lower stratosphere shows increased ozone, while a small negative ozone anomaly appears in the lowermost stratosphere. These differences are related to contributions due to anomalous adiabatic vertical motion, which are implicit in potential temperature coordinates. Our analyses of the ozone budget in the extratropical middle stratosphere show that the polar ozone response maximum around 600 K and the negative anomalies around 450 K beneath both reflect the combined effects of anomalous diabatic downwelling and quasi-isentropic eddy mixing, which are associated with consecutive counteracting anomalous ozone tendencies on daily timescales. We find that approx. 71 % of the total variability in polar column ozone in the stratosphere is associated with year-by-year variations in polar vortex strength based on ERA5 reanalyses for the winter seasons 1980–2022. MLS observations for 2005–2020 show that around 86 % can be explained by these co-variations with the polar vortex.

The number of large urban agglomerations is steadily increasing worldwide. At a local scale, their emissions lead to air pollution, directly affecting people's health. On a global scale, their emissions lead to an increase of greenhouse gases, affecting climate. In this context, in 2017 and 2018, the airborne campaign EMeRGe (Effect of Megacities on the transport and transformation of pollutants on the Regional to Global scales) investigated emissions of European and Asian major population centres (MPCs) to improve the understanding and predictability of pollution outflows. Here, we present two methods to identify and characterise pollution outflows probed during EMeRGe. First, we use a set of volatile organic compounds (VOCs) as chemical tracers to characterise air masses by specific source signals, i.e. benzene from anthropogenic pollution of targeted regions, acetonitrile from biomass burning (BB, primarily during EMeRGe-Asia), and isoprene from fresh biogenic signals (primarily during EMeRGe-Europe. Second, we attribute probed air masses to source regions and estimate their individual contribution by constructing and applying a simple emission uptake scheme for the boundary layer which combines FLEXTRA back trajectories and EDGAR carbon monoxide (CO) emission rates (acronyms are provided in the Appendix). During EMeRGe-Europe, we identified anthropogenic pollution outflows from northern Italy, southern Great Britain, the Belgium–Netherlands–Ruhr (BNR) area and the Iberian Peninsula. Additionally, our uptake scheme indicates significant long-range transport of pollution from the USA and Canada. During EMeRGe-Asia, the pollution outflow is dominated by sources in China and Taiwan, but BB signals from Southeast Asia and India contribute as well. Outflows of pre-selected MPC targets are identified in less than 20 % of the sampling time, due to restrictions in flight planning and constraints of the measurement platform itself. Still, EMeRGe combines in a unique way near- and far-field measurements, which show signatures of local and distant sources, transport and conversion fingerprints, and complex air mass compositions. Our approach provides a valuable classification and characterisation of the EMeRGe dataset, e.g. for BB and anthropogenic influence of potential source regions and paves the way for a more comprehensive analysis and various model studies.

Megacities and other major population centres (MPCs) worldwide are major sources of air pollution, both locally as well as downwind. The overall assessment and prediction of the impact of MPC pollution on tropospheric chemistry are challenging. The present work provides an overview of the highlights of a major new contribution to the understanding of this issue based on the data and analysis of the EMeRGe (Effect of Megacities on the transport and transformation of pollutants on the Regional to Global scales) international project. EMeRGe focuses on atmospheric chemistry, dynamics, and transport of local and regional pollution originating in MPCs. Airborne measurements, taking advantage of the long range capabilities of the High Altitude and LOng Range Research Aircraft (HALO, https://www.halo-spp.de, last access: 22 March 2022), are a central part of the project. The synergistic use and consistent interpretation of observational data sets of different spatial and temporal resolution (e.g. from ground-based networks, airborne campaigns, and satellite measurements) supported by modelling within EMeRGe provide unique insight to test the current understanding of MPC pollution outflows. In order to obtain an adequate set of measurements at different spatial scales, two field experiments were positioned in time and space to contrast situations when the photochemical transformation of plumes emerging from MPCs is large. These experiments were conducted in summer 2017 over Europe and in the inter-monsoon period over Asia in spring 2018. The intensive observational periods (IOPs) involved HALO airborne measurements of ozone and its precursors, volatile organic compounds, aerosol particles, and related species as well as coordinated ground-based ancillary observations at different sites. Perfluorocarbon (PFC) tracer releases and model forecasts supported the flight planning, the identification of pollution plumes, and the analysis of chemical transformations during transport. This paper describes the experimental deployment and scientific questions of the IOP in Europe. The MPC targets – London (United Kingdom; UK), the Benelux/Ruhr area (Belgium, the Netherlands, Luxembourg and Germany), Paris (France), Rome and the Po Valley (Italy), and Madrid and Barcelona (Spain) – were investigated during seven HALO research flights with an aircraft base in Germany for a total of 53 flight hours. An in-flight comparison of HALO with the collaborating UK-airborne platform Facility for Airborne Atmospheric Measurements (FAAM) took place to assure accuracy and comparability of the instrumentation on board. Overall, EMeRGe unites measurements of near- and far-field emissions and hence deals with complex air masses of local and distant sources. Regional transport of several European MPC outflows was successfully identified and measured. Chemical processing of the MPC emissions was inferred from airborne observations of primary and secondary pollutants and the ratios between species having different chemical lifetimes. Photochemical processing of aerosol and secondary formation or organic acids was evident during the transport of MPC plumes. Urban plumes mix efficiently with natural sources as mineral dust and with biomass burning emissions from vegetation and forest fires. This confirms the importance of wildland fire emissions in Europe and indicates an important but discontinuous contribution to the European emission budget that might be of relevance in the design of efficient mitigation strategies. The present work provides an overview of the most salient results in the European context, with these being addressed in more detail within additional dedicated EMeRGe studies. The deployment and results obtained in Asia will be the subject of separate publications.

The upper troposphere and lower stratosphere (UTLS) region during the summer monsoon season over North America (NAM) is influenced by the transport of air from a variety of source regions over a wide range of timescales (hours to years). Age spectra are useful for characterizing the transport into such a region, and in this study we use and build on recently developed techniques to infer age spectra from trace gas measurements with photochemical lifetimes from days to centuries. We show that the measurements taken by the whole-air sampler instrument during the SEAC4RS campaign can be used to derive not only age spectra, but also path-integrated lifetimes of each of the trace gases and partitioning between North American and tropical surface source origins. The method used here can also clearly identify and adjust for measurement outliers that were influenced by polluted surface source regions. The results are generally consistent with expected transport features of the NAM but also provide a range of transport diagnostics (age spectra, trace gas lifetimes and surface source regions) that have not previously been computed solely from in situ measurements. These methods may be applied to many other existing in situ datasets, and the transport diagnostics can be compared with chemistry–climate model transport in the UTLS.

This paper presents a modelling study on the fate of CHBr3 and its product gases in the troposphere within the context of tropical deep convection. A cloud-scale case study was conducted along the west coast of Borneo, where several deep convective systems were triggered on the afternoon and early evening of 19 November 2011. These systems were sampled by the Falcon aircraft during the field campaign of the SHIVA project and analysed using a simulation with the cloud-resolving meteorological model C-CATT-BRAMS at 2×2 km resolution that represents the emissions, transport by large-scale flow, convection, photochemistry, and washout of CHBr3 and its product gases (PGs). We find that simulated CHBr3 mixing ratios and the observed values in the boundary layer and the outflow of the convective systems agree. However, the model underestimates the background CHBr3 mixing ratios in the upper troposphere, which suggests a missing source at the regional scale. An analysis of the simulated chemical speciation of bromine within and around each simulated convective system during the mature convective stage reveals that >85 % of the bromine derived from CHBr3 and its PGs is transported vertically to the point of convective detrainment in the form of CHBr3 and that the remaining small fraction is in the form of organic PGs, principally insoluble brominated carbonyls produced from the photo-oxidation of CHBr3. The model simulates that within the boundary layer and free troposphere, the inorganic PGs are only present in soluble forms, i.e. HBr, HOBr, and BrONO2, and, consequently, within the convective clouds, the inorganic PGs are almost entirely removed by wet scavenging. We find that HBr is the most abundant PG in background lower-tropospheric air and that this prevalence of HBr is a result of the relatively low background tropospheric ozone levels at the regional scale. Contrary to a previous study in a different environment, for the conditions in the simulation, the insoluble Br2 species is hardly formed within the convective systems and therefore plays no significant role in the vertical transport of bromine. This likely results from the relatively small quantities of simulated inorganic bromine involved, the presence of HBr in large excess compared to HOBr and BrO, and the relatively efficient removal of soluble compounds within the convective column.

Derivation of mean age of air (AoA) and age spectra from atmospheric measurements remains a challenge and often requires output from atmospheric models. This study tries to minimize the direct influence of model output and presents an extension and application of a previously established inversion method to derive age spectra from mixing ratios of long- and short-lived trace gases. For a precise description of cross-tropopause transport processes, the inverse method is extended to incorporate air entrainment into the stratosphere across the tropical and extratropical tropopause. We first use simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) to provide a general proof of concept of the extended principle in a controllable and consistent environment, where the method is applied to an idealized set of 10 trace gases with predefined constant lifetimes and compared to reference model age spectra. In the second part of the study we apply the extended inverse method to atmospheric measurements of multiple long- and short-lived trace gases measured aboard the High Altitude and Long Range (HALO) research aircraft during the two research campaigns POLSTRACC–GW-LCYCLE–SALSA (PGS) and Wave-driven Isentropic Exchange (WISE). As some of the observed species undergo significant loss processes in the stratosphere, a Monte Carlo simulation is introduced to retrieve age spectra and chemical lifetimes in stepwise fashion and to account for the large uncertainties. Results show that in the idealized model scenario the inverse method retrieves age spectra robustly on annual and seasonal scales. The extension to multiple entry regions proves reasonable as our CLaMS simulations reveal that in the model between 50 % and 70 % of air in the lowermost stratosphere has entered through the extratropical tropopause (30–90∘ N and S) on annual average. When applied to observational data of PGS and WISE, the method derives age spectra and mean AoA with meaningful spatial distributions and quantitative range, yet large uncertainties. Results indicate that entrainment of fresh tropospheric air across both the extratropical and tropical tropopause peaked prior to both campaigns, but with lower mean AoA for WISE than PGS data. The ratio of moments for all retrieved age spectra for PGS and WISE is found to range between 0.52 and 2.81 years. We conclude that the method derives reasonable and consistent age spectra using observations of chemically active trace gases. Our findings might contribute to an improved assessment of transport with age spectra in future studies.

Mean age of air (AoA) is a diagnostic of transport along the stratospheric Brewer–Dobson circulation. While models consistently show negative trends, long-term time series (1975–2016) of AoA derived from observations show non-significant positive trends in mean AoA in the Northern Hemisphere. This discrepancy between observed and modelled mean AoA trends is still not resolved. There are uncertainties and assumptions required when deriving AoA from trace gas observations. At the same time, AoA from climate models is subject to uncertainties, too. In this paper, we focus on the uncertainties due to the parameter selection in the method that is used to derive mean AoA from SF6 measurements in Engel et al. (2009, 2017). To correct for the non-linear increase in SF6 concentrations, a quadratic fit to the time series at the reference location, i.e. the tropical surface, is used. For this derivation, the width of the AoA distribution (age spectrum) has to be assumed. In addition, to choose the number of years the quadratic fit is performed for, the fraction of the age spectrum to be considered has to be assumed. Even though the uncertainty range due to all different aspects has already been taken into account for the total errors in the AoA values, the systematic influence of the parameter selection on AoA trends is described for the first time in the present study. For this, we use the EMAC (ECHAM MESSy Atmospheric Chemistry) climate model as a test bed, where AoA derived from a linear tracer is available as a reference and modelled age spectra exist to diagnose the actual spatial age spectra widths. The comparison of mean AoA from the linear tracer with mean AoA from a SF6 tracer shows systematic deviations specifically in the trends due to the selection of the parameters. However, for an appropriate parameter selection, good agreement for both mean AoA and its trend can be found, with deviations of about 1 % in mean AoA and 12 % in AoA trend. In addition, a method to derive mean AoA is evaluated that applies a convolution to the reference time series. The resulting mean AoA and its trend only depend on an assumption about the ratio of moments. Also in that case, it is found that the larger the ratio of moments, the more the AoA trend gravitates towards the negative. The linear tracer and SF6 AoA are found to agree within 0.3 % in the mean and 6 % in the trend. The different methods and parameter selections were then applied to the balloon-borne SF6 and CO2 observations. We found the same systematic changes in mean AoA trend dependent on the specific selection. When applying a parameter choice that is suggested by the model results, the AoA trend is reduced from 0.15 to 0.07 years per decade. It illustrates that correctly constraining those parameters is crucial for correct mean AoA and trend estimates and still remains a challenge in the real atmosphere.

We present novel measurements of five short-lived brominated source gases (CH2Br2, CHBr3, CH2ClBr, CHCl2Br and CHClBr2). These rather short-lived gases are an important source of bromine to the stratosphere, where they can lead to depletion of ozone. The measurements have been obtained using an in situ gas chromatography and mass spectrometry (GC–MS) system on board the High Altitude and Long Range Research Aircraft (HALO). The instrument is extremely sensitive due to the use of chemical ionization, allowing detection limits in the lower parts per quadrillion (ppq, 10−15) range. Data from three campaigns using HALO are presented, where the upper troposphere and lower stratosphere (UTLS) of the northern hemispheric mid-to-high latitudes were sampled during winter and during late summer to early fall. We show that an observed decrease with altitude in the stratosphere is consistent with the relative lifetimes of the different compounds. Distributions of the five source gases and total organic bromine just below the tropopause show an increase in mixing ratio with latitude, in particular during polar winter. This increase in mixing ratio is explained by increasing lifetimes at higher latitudes during winter. As the mixing ratios at the extratropical tropopause are generally higher than those derived for the tropical tropopause, extratropical troposphere-to-stratosphere transport will result in elevated levels of organic bromine in comparison to air transported over the tropical tropopause. The observations are compared to model estimates using different emission scenarios. A scenario with emissions mainly confined to low latitudes cannot reproduce the observed latitudinal distributions and will tend to overestimate organic bromine input through the tropical tropopause from CH2Br2 and CHBr3. Consequently, the scenario also overestimates the amount of brominated organic gases in the stratosphere. The two scenarios with the highest overall emissions of CH2Br2 tend to overestimate mixing ratios at the tropical tropopause, but they are in much better agreement with extratropical tropopause mixing ratios. This shows that not only total emissions but also latitudinal distributions in the emissions are of importance. While an increase in tropopause mixing ratios with latitude is reproduced with all emission scenarios during winter, the simulated extratropical tropopause mixing ratios are on average lower than the observations during late summer to fall. We show that a good knowledge of the latitudinal distribution of tropopause mixing ratios and of the fractional contributions of tropical and extratropical air is needed to derive stratospheric inorganic bromine in the lowermost stratosphere from observations. In a sensitivity study we find maximum differences of a factor 2 in inorganic bromine in the lowermost stratosphere from source gas injection derived from observations and model outputs. The discrepancies depend on the emission scenarios and the assumed contributions from different source regions. Using better emission scenarios and reasonable assumptions on fractional contribution from the different source regions, the differences in inorganic bromine from source gas injection between model and observations is usually on the order of 1 ppt or less. We conclude that a good representation of the contributions of different source regions is required in models for a robust assessment of the role of short-lived halogen source gases on ozone depletion in the UTLS.

Climate models consistently predict an acceleration of the Brewer–Dobson circulation (BDC) due to climate change in the 21st century. However, the strength of this acceleration varies considerably among individual models, which constitutes a notable source of uncertainty for future climate projections. To shed more light upon the magnitude of this uncertainty and on its causes, we analyse the stratospheric mean age of air (AoA) of 10 climate projection simulations from the Chemistry-Climate Model Initiative phase 1 (CCMI-I), covering the period between 1960 and 2100. In agreement with previous multi-model studies, we find a large model spread in the magnitude of the AoA trend over the simulation period. Differences between future and past AoA are found to be predominantly due to differences in mixing (reduced aging by mixing and recirculation) rather than differences in residual mean transport. We furthermore analyse the mixing efficiency, a measure of the relative strength of mixing for given residual mean transport, which was previously hypothesised to be a model constant. Here, the mixing efficiency is found to vary not only across models, but also over time in all models. Changes in mixing efficiency are shown to be closely related to changes in AoA and quantified to roughly contribute 10 % to the long-term AoA decrease over the 21st century. Additionally, mixing efficiency variations are shown to considerably enhance model spread in AoA changes. To understand these mixing efficiency variations, we also present a consistent dynamical framework based on diffusive closure, which highlights the role of basic state potential vorticity gradients in controlling mixing efficiency and therefore aging by mixing.

In late 2013, a whole air flask collection programme was started at Taunus Observatory (TO) in central Germany. Being a rural site in close proximity to the Rhine–Main area, Taunus Observatory allows assessment of emissions from a densely populated region. Owing to its altitude of 825 m, the site also regularly experiences background conditions, especially when air masses approach from north-westerly directions. With a large footprint area mainly covering central Europe north of the Alps, halocarbon measurements at the site have the potential to improve the database for estimation of regional and total European halogenated greenhouse gas emissions. Flask samples are collected weekly for offline analysis using a GC/MS system simultaneously employing a quadrupole as well as a time-of-flight mass spectrometer. As background reference, additional samples are collected approximately once every 2 weeks at the Mace Head Atmospheric Research Station (MHD) when air masses approach from the site's clean air sector. Thus the time series at TO can be linked to the in situ AGAGE measurements and the NOAA flask sampling programme at MHD. An iterative baseline identification procedure separates polluted samples from baseline data. While there is good agreement of baseline mixing ratios between TO and MHD, with a larger variability of mixing ratios at the continental site, measurements at TO are regularly influenced by elevated halocarbon mixing ratios. Here, first time series are presented for CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-227ea, HFC-245fa, and dichloromethane. While atmospheric mixing ratios of the chlorofluorocarbons (CFCs) decrease, they increase for the hydrochlorofluorocarbons (HCFCs) and the hydrofluorocarbons (HFCs). Small unexpected differences between CFC-11 and CFC-12 are found with regard to frequency and relative enhancement of high mixing ratio events and seasonality, although production and use of both compounds are strictly regulated by the Montreal Protocol, and therefore a similar decrease in atmospheric mixing ratios should occur. Dichloromethane, a solvent about which recently concerns have been raised regarding its growing influence on stratospheric ozone depletion, does not show a significant trend with regard to both baseline mixing ratios and the occurrence of pollution events at Taunus Observatory for the time period covered, indicating stable emissions in the regions that influence the site. An analysis of trajectories from the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model reveals differences in halocarbon mixing ranges depending on air mass origin.

Mercury was measured onboard the IAGOS-CARIBIC passenger aircraft from May 2005 until February 2016 during near monthly sequences of mostly four intercontinental flights from Germany to destinations in North and South America, Africa and South and East Asia. Most of these mercury data were obtained using an internal default signal integration procedure of the Tekran instrument but since April 2014 more precise and accurate data were obtained using post-flight manual integration of the instrument raw signal. In this paper we use the latter data.Increased upper tropospheric total mercury (TM) concentrations due to large scale biomass burning were observed in the upper troposphere (UT) at the equator and southern latitudes during the flights to Latin America and South Africa in boreal autumn (SON) and boreal winter (DJF). TM concentrations in the lowermost stratosphere (LMS) decrease with altitude above the thermal tropopause but the gradient is less steep than reported before. Seasonal variation of the vertical TM distribution in the UT and LMS is similar to that of other trace gases with surface sources and stratospheric sinks. Speciation experiments suggest comparable TM and gaseous elementary mercury (GEM) concentrations at and below the tropopause leaving little space for Hg2+ (TM − GEM) being the dominating component of TM here. In the stratosphere significant GEM concentrations were found to exist up to 4 km altitude above the thermal tropopause. Correlations with N2O as a reference tracer suggest stratospheric lifetimes of 72±37 and 74±27 years for TM and GEM, respectively, comparable to the stratospheric lifetime of COS. This coincidence, combined with pieces of evidence from us and other researchers, corroborates the hypothesis that Hg2+ formed by oxidation in the stratosphere attaches to sulfate particles formed mainly by oxidation of COS and is removed with them from the stratosphere by air mass exchange, gravitational sedimentation and cloud scavenging processes.

We present data from winter 2015–2016, which were measured during the POLSTRACC (The Polar Stratosphere in a Changing Climate) aircraft campaign between December 2015 and March 2016 in the Arctic upper troposphere and lower stratosphere (UTLS). The focus of this work is on the role of transport and mixing between aged and potentially chemically processed air masses from the stratosphere which have midlatitude and low-latitude air mass fractions with small transit times originating at the tropical lower stratosphere. By combining measurements of CO, N2O and SF6 we estimate the evolution of the relative contributions of transport and mixing to the UTLS composition over the course of the winter. We find an increasing influence of aged stratospheric air partly from the vortex as indicated by decreasing N2O and SF6 values over the course of the winter in the extratropical lower and lowermost stratosphere between Θ = 360 K and Θ = 410 K over the North Atlantic and the European Arctic. Surprisingly we also found a mean increase in CO of (3.00 ± 1.64) ppbV from January to March relative to N2O in the lower stratosphere. We show that this increase in CO is consistent with an increased mixing of tropospheric air as part of the fast transport mechanism in the lower stratosphere surf zone. The analysed air masses were partly affected by air masses which originated at the tropical tropopause and were quasi-horizontally mixed into higher latitudes. This increase in the tropospheric air fraction partly compensates for ageing of the UTLS due to the diabatic descent of air masses from the vortex by horizontally mixed, tropospheric-influenced air masses. This is consistent with simulated age spectra from the Chemical Lagrangian Model of the Stratosphere (CLaMS), which show a respective fractional increase in tropospheric air with transit times under 6 months and a simultaneous increase in aged air from upper stratospheric and vortex regions with transit times longer than 2 years. We thus conclude that the lowermost stratosphere in winter 2015–2016 was affected by aged air from the upper stratosphere and vortex region. These air masses were significantly affected by increased mixing from the lower latitudes, which led to a simultaneous increase in the fraction of young air in the lowermost Arctic stratosphere by 6 % from January to March 2016.

In a changing climate, potential stratospheric circulation changes require long-term monitoring. Stratospheric trace gas measurements are often used as a proxy for stratospheric circulation changes via the mean age of air values derived from them. In this study, we investigated five potential age of air tracers – the perfluorocarbons CF4, C2F6 and C3F8 and the hydrofluorocarbons CHF3 (HFC-23) and HFC-125 – and compare them to the traditional tracer SF6 and a (relatively) shorter-lived species, HFC-227ea. A detailed uncertainty analysis was performed on mean ages derived from these new tracers to allow us to confidently compare their efficacy as age tracers to the existing tracer, SF6. Our results showed that uncertainties associated with the mean age derived from these new age tracers are similar to those derived from SF6, suggesting that these alternative compounds are suitable in this respect for use as age tracers. Independent verification of the suitability of these age tracers is provided by a comparison between samples analysed at the University of East Anglia and the Scripps Institution of Oceanography. All five tracers give younger mean ages than SF6, a discrepancy that increases with increasing mean age. Our findings qualitatively support recent work that suggests that the stratospheric lifetime of SF6 is significantly less than the previous estimate of 3200 years. The impact of these younger mean ages on three policy-relevant parameters – stratospheric lifetimes, fractional release factors (FRFs) and ozone depletion potentials – is investigated in combination with a recently improved methodology to calculate FRFs. Updates to previous estimations for these parameters are provided.

Chlorine and bromine atoms lead to catalytic depletion of ozone in the stratosphere. Therefore the use and production of ozone-depleting substances (ODSs) containing chlorine and bromine is regulated by the Montreal Protocol to protect the ozone layer. Equivalent effective stratospheric chlorine (EESC) has been adopted as an appropriate metric to describe the combined effects of chlorine and bromine released from halocarbons on stratospheric ozone. Here we revisit the concept of calculating EESC. We derive a refined formulation of EESC based on an advanced concept of ODS propagation into the stratosphere and reactive halogen release. A new transit time distribution is introduced in which the age spectrum for an inert tracer is weighted with the release function for inorganic halogen from the source gases. This distribution is termed the release time distribution. We show that a much better agreement with inorganic halogen loading from the chemistry transport model TOMCAT is achieved compared with using the current formulation. The refined formulation shows EESC levels in the year 1980 for the mid-latitude lower stratosphere, which are significantly lower than previously calculated. The year 1980 is commonly used as a benchmark to which EESC must return in order to reach significant progress towards halogen and ozone recovery. Assuming that – under otherwise unchanged conditions – the EESC value must return to the same level in order for ozone to fully recover, we show that it will take more than 10 years longer than estimated in this region of the stratosphere with the current method for calculation of EESC. We also present a range of sensitivity studies to investigate the effect of changes and uncertainties in the fractional release factors and in the assumptions on the shape of the release time distributions. We further discuss the value of EESC as a proxy for future evolution of inorganic halogen loading under changing atmospheric dynamics using simulations from the EMAC model. We show that while the expected changes in stratospheric transport lead to significant differences between EESC and modelled inorganic halogen loading at constant mean age, EESC is a reasonable proxy for modelled inorganic halogen on a constant pressure level.

An original and innovative sampling system called AirCore was presented by NOAA in 2010 (Karion et al., 2010). It consists of a long (> 100 m) and narrow (2 and CH4, (ii) provide a tool to compare AirCores and validate the estimated vertical resolution achieved by AirCores. This (high-resolution) AirCore-HR consists of a 300 m tube, combining 200 m of 0.125 in. (3.175 mm) tube and a 100 m of 0.25 in. (6.35 mm) tube. This new configuration allows us to achieve a vertical resolution of 300 m up to 15 km and better than 500 m up to 22 km (if analysis of the retained sample is performed within 3 h). The AirCore-HR was flown for the first time during the annual StratoScience campaign from CNES in August 2014 from Timmins (Ontario, Canada). High-resolution vertical profiles of CO2 and CH4 up to 25 km were successfully retrieved. These profiles revealed well-defined transport structures in the troposphere (also seen in CAMS-ECMWF high-resolution forecasts of CO2 and CH4 profiles) and captured the decrease of CO2 and CH4 in the stratosphere. The multi-instrument gondola also carried two other low-resolution AirCore-GUF that allowed us to perform direct comparisons and study the underlying processing method used to convert the sample of air to greenhouse gases vertical profiles. In particular, degrading the AirCore-HR derived profiles to the low resolution of AirCore-GUF yields an excellent match between both sets of CH4 profiles and shows a good consistency in terms of vertical structures. This fully validates the theoretical vertical resolution achievable by AirCores. Concerning CO2 although a good agreement is found in terms of vertical structure, the comparison between the various AirCores yields a large and variable bias (up to almost 3 ppm in some parts of the profiles). The reasons of this bias, possibly related to the drying agent used to dry the air, are still being investigated. Finally, the uncertainties associated with the measurements are assessed, yielding an average uncertainty below 3 ppb for CH4 and 0.25 ppm for CO2 with the major source of uncertainty coming from the potential loss of air sample on the ground and the choice of the starting and ending point of the collected air sample inside the tube. In an ideal case where the sample would be fully retained, it would be possible to know precisely the pressure at which air was sampled last and thus to improve the overall uncertainty to about 0.1 ppm for CO2 and 2 ppb for CH4.

Mean age of stratospheric air can be derived from observations of sufficiently long-lived trace gases with approximately linear trends in the troposphere. Mean age can serve as a tracer to investigate stratospheric transport and long-term changes in the strength of the overturning Brewer–Dobson circulation of the stratosphere. For this purpose, a low-cost method is required in order to allow for regular observations up to altitudes of about 30 km. Despite the desired low costs, high precision and accuracy are required in order to determine mean age. We present balloon-borne AirCore observations from two midlatitude sites: Timmins in Ontario/Canada and Lindenberg in Germany. During the Timmins campaign, five AirCores sampled air in parallel with a large stratospheric balloon and were analysed for CO2, CH4 and partly CO. We show that there is good agreement between the different AirCores (better than 0.1 %), especially when vertical gradients are small. The measurements from Lindenberg were performed using small low-cost balloons and yielded very comparable results. We have used the observations to extend our long-term data set of mean age observations at Northern Hemisphere midlatitudes. The time series now covers more than 40 years and shows a small, statistically non-significant positive trend of 0.15 ± 0.18 years decade−1. This trend is slightly smaller than the previous estimate of 0.24 ± 0.22 years decade−1 which was based on observations up to the year 2006. These observations are still in contrast to strong negative trends of mean age as derived from some model calculations.

The fractional release factor (FRF) gives information on the amount of a halocarbon that is released at some point into the stratosphere from its source form to the inorganic form, which can harm the ozone layer through catalytic reactions. The quantity is of major importance because it directly affects the calculation of the ozone depletion potential (ODP). In this context time-independent values are needed which, in particular, should be independent of the trends in the tropospheric mixing ratios (tropospheric trends) of the respective halogenated trace gases. For a given atmospheric situation, such FRF values would represent a molecular property.We analysed the temporal evolution of FRF from ECHAM/MESSy Atmospheric Chemistry (EMAC) model simulations for several halocarbons and nitrous oxide between 1965 and 2011 on different mean age levels and found that the widely used formulation of FRF yields highly time-dependent values. We show that this is caused by the way that the tropospheric trend is handled in the widely used calculation method of FRF.Taking into account chemical loss in the calculation of stratospheric mixing ratios reduces the time dependence in FRFs. Therefore we implemented a loss term in the formulation of the FRF and applied the parameterization of a mean arrival time to our data set.We find that the time dependence in the FRF can almost be compensated for by applying a new trend correction in the calculation of the FRF. We suggest that this new method should be used to calculate time-independent FRFs, which can then be used e.g. for the calculation of ODP.

Acetone and carbon monoxide (CO) are two important trace gases controlling the oxidation capacity of the troposphere; enhancement ratios (EnRs) are useful in assessing their sources and fate between emission and sampling, especially in pollution plumes. In this study, we focus on in situ data from the upper troposphere recorded by the passenger-aircraft-based IAGOS–CARIBIC (In-service Aircraft for a Global Observing System–Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) observatory over the periods 2006–2008 and 2012–2015. This dataset is used to investigate the seasonal and spatial variation of acetone–CO EnRs. Furthermore, we utilize a box model accounting for dilution, chemical degradation and secondary production of acetone from precursors. In former studies, increasing acetone–CO EnRs in a plume were associated with secondary production of acetone. Results of our box model question this common presumption and show increases of acetone–CO EnR over time without taking secondary production of acetone into account. The temporal evolution of EnRs in the upper troposphere, especially in summer, is not negligible and impedes the interpretation of EnRs as a means for partitioning of acetone and CO sources in the boundary layer. In order to ensure that CARIBIC EnRs represent signatures of source regions with only small influences by dilution and chemistry, we limit our analysis to temporal and spatial coherent events of high-CO enhancement. We mainly focus on North America and Southeast Asia because of their different mix of pollutant sources and the good data coverage. For both regions, we find the expected seasonal variation in acetone–CO EnRs with maxima in summer, but with higher amplitude over North America. We derive mean (± standard deviation) annual acetone fluxes of (53 ± 27) 10−13 kg m−2 s−1 and (185 ± 80) 10−13 kg m−2 s−1 for North America and Southeast Asia, respectively. The derived flux for North America is consistent with the inventories, whereas Southeast Asia acetone emissions appear to be underestimated by the inventories.

We present a compact and versatile cryofocusing–thermodesorption unit, which we developed for quantitative analysis of halogenated trace gases in ambient air. Possible applications include aircraft-based in situ measurements, in situ monitoring and laboratory operation for the analysis of flask samples. Analytes are trapped on adsorptive material cooled by a Stirling cooler to low temperatures (e.g. −80 °C) and subsequently desorbed by rapid heating of the adsorptive material (e.g. +200 °C). The set-up involves neither the exchange of adsorption tubes nor any further condensation or refocusing steps. No moving parts are used that would require vacuum insulation. This allows for a simple and robust design. Reliable operation is ensured by the Stirling cooler, which neither contains a liquid refrigerant nor requires refilling a cryogen. At the same time, it allows for significantly lower adsorption temperatures compared to commonly used Peltier elements. We use gas chromatography – mass spectrometry (GC–MS) for separation and detection of the preconcentrated analytes after splitless injection. A substance boiling point range of approximately −80 to +150 °C and a substance mixing ratio range of less than 1 ppt (pmol mol−1) to more than 500 ppt in preconcentrated sample volumes of 0.1 to 10 L of ambient air is covered, depending on the application and its analytical demands. We present the instrumental design of the preconcentration unit and demonstrate capabilities and performance through the examination of analyte breakthrough during adsorption, repeatability of desorption and analyte residues in blank tests. Examples of application are taken from the analysis of flask samples collected at Mace Head Atmospheric Research Station in Ireland using our laboratory GC–MS instruments and by data obtained during a research flight with our in situ aircraft instrument GhOST-MS (Gas chromatograph for the Observation of Tracers – coupled with a Mass Spectrometer).

The transport of air masses originating from the Asian monsoon anticyclone into the extratropical upper troposphere and lower stratosphere (Ex-UTLS) above potential temperatures Θ = 380 K was identified during the HALO aircraft mission TACTS in August and September 2012. In situ measurements of CO, O3 and N2O during TACTS flight 2 on 30 August 2012 show the irreversible mixing of aged stratospheric air masses with younger (recently transported from the troposphere) ones within the Ex-UTLS. Backward trajectories calculated with the trajectory module of CLaMS indicate that these tropospherically affected air masses originate from the Asian monsoon anticyclone. These air masses are subsequently transported above potential temperatures Θ = 380 K from the monsoon circulation region into the Ex-UTLS, where they subsequently mix with stratospheric air masses. The overall trace gas distribution measured during TACTS shows that this transport pathway had affected the chemical composition of the Ex-UTLS during boreal summer and autumn 2012. This leads to an intensification of the tropospheric influence on the extratropical lower stratosphere with PV > 8 pvu within 3 weeks during the TACTS mission. During the same time period a weakening of the tropospheric influence on the lowermost stratosphere (LMS) is determined. The study shows that the transport of air masses originating from the Asian summer monsoon region within the lower stratosphere affects the change in the chemical composition of the Ex-UTLS over Europe and thus contributes to the flushing of the LMS during summer 2012.

The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry–climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993–2012). Except for three model simulations, all others were driven offline by (or nudged to) reanalysed meteorology. The overarching goal of TransCom-VSLS was to provide a reconciled model estimate of the stratospheric source gas injection (SGI) of bromine from these gases, to constrain the current measurement-derived range, and to investigate inter-model differences due to emissions and transport processes. Models ran with standardised idealised chemistry, to isolate differences due to transport, and we investigated the sensitivity of results to a range of VSLS emission inventories. Models were tested in their ability to reproduce the observed seasonal and spatial distribution of VSLS at the surface, using measurements from NOAA's long-term global monitoring network, and in the tropical troposphere, using recent aircraft measurements – including high-altitude observations from the NASA Global Hawk platform. The models generally capture the observed seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model–measurement correlation (r ≥ 0.7) at most sites. In a given model, the absolute model–measurement agreement at the surface is highly sensitive to the choice of emissions. Large inter-model differences are apparent when using the same emission inventory, highlighting the challenges faced in evaluating such inventories at the global scale. Across the ensemble, most consistency is found within the tropics where most of the models (8 out of 11) achieve best agreement to surface CHBr3 observations using the lowest of the three CHBr3 emission inventories tested (similarly, 8 out of 11 models for CH2Br2). In general, the models reproduce observations of CHBr3 and CH2Br2 obtained in the tropical tropopause layer (TTL) at various locations throughout the Pacific well. Zonal variability in VSLS loading in the TTL is generally consistent among models, with CHBr3 (and to a lesser extent CH2Br2) most elevated over the tropical western Pacific during boreal winter. The models also indicate the Asian monsoon during boreal summer to be an important pathway for VSLS reaching the stratosphere, though the strength of this signal varies considerably among models. We derive an ensemble climatological mean estimate of the stratospheric bromine SGI from CHBr3 and CH2Br2 of 2.0 (1.2–2.5) ppt, ∼ 57 % larger than the best estimate from the most recent World Meteorological Organization (WMO) Ozone Assessment Report. We find no evidence for a long-term, transport-driven trend in the stratospheric SGI of bromine over the simulation period. The transport-driven interannual variability in the annual mean bromine SGI is of the order of ±5 %, with SGI exhibiting a strong positive correlation with the El Niño–Southern Oscillation (ENSO) in the eastern Pacific. Overall, our results do not show systematic differences between models specific to the choice of reanalysis meteorology, rather clear differences are seen related to differences in the implementation of transport processes in the models.

MIPAS-Envisat is a satellite-borne sensor which measured vertical profiles of a wide range of trace gases from 2002 to 2012 using IR emission spectroscopy. We present geophysical validation of the MIPAS-Envisat operational retrieval (version 6.0) of N2O, CH4, CFC-12, and CFC-11 by the European Space Agency (ESA). The geophysical validation data are derived from measurements of samples collected by a cryogenic whole air sampler flown to altitudes of up to 34 km by means of large scientific balloons. In order to increase the number of coincidences between the satellite and the balloon observations, we applied a trajectory matching technique. The results are presented for different time periods due to a change in the spectroscopic resolution of MIPAS in early 2005. Retrieval results for N2O, CH4, and CFC-12 show partly good agreement for some altitude regions, which differs for the periods with different spectroscopic resolution. The more recent low spectroscopic resolution data above 20 km altitude show agreement with the combined uncertainties, while there is a tendency of the earlier high spectral resolution data set to underestimate these species above 25 km. The earlier high spectral resolution data show a significant overestimation of the mixing ratios for N2O, CH4, and CFC-12 below 20 km. These differences need to be considered when using these data. The CFC-11 results from the operation retrieval version 6.0 cannot be recommended for scientific studies due to a systematic overestimation of the CFC-11 mixing ratios at all altitudes.

We present the characterization and application of a new gas chromatography time-of-flight mass spectrometry instrument (GC-TOFMS) for the quantitative analysis of halocarbons in air samples. The setup comprises three fundamental enhancements compared to our earlier work (Hoker et al., 2015): (1) full automation, (2) a mass resolving power R = m/Δm of the TOFMS (Tofwerk AG, Switzerland) increased up to 4000 and (3) a fully accessible data format of the mass spectrometric data. Automation in combination with the accessible data allowed an in-depth characterization of the instrument. Mass accuracy was found to be approximately 5 ppm in mean after automatic recalibration of the mass axis in each measurement. A TOFMS configuration giving R = 3500 was chosen to provide an R-to-sensitivity ratio suitable for our purpose. Calculated detection limits are as low as a few femtograms by means of the accurate mass information. The precision for substance quantification was 0.15 % at the best for an individual measurement and in general mainly determined by the signal-to-noise ratio of the chromatographic peak. Detector non-linearity was found to be insignificant up to a mixing ratio of roughly 150 ppt at 0.5 L sampled volume. At higher concentrations, non-linearities of a few percent were observed (precision level: 0.2 %) but could be attributed to a potential source within the detection system. A straightforward correction for those non-linearities was applied in data processing, again by exploiting the accurate mass information. Based on the overall characterization results, the GC-TOFMS instrument was found to be very well suited for the task of quantitative halocarbon trace gas observation and a big step forward compared to scanning, quadrupole MS with low mass resolving power and a TOFMS technique reported to be non-linear and restricted by a small dynamical range.

Marine-produced short-lived trace gases such as dibromomethane (CH2Br2), bromoform (CHBr3), methyliodide (CH3I) and dimethyl sulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry) with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model real-time conditions at the ocean surface and in the atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of very short-lived substances (VSLS). We show that differences between prescribing emissions and prescribing concentrations (−28 % for CH2Br2 to +11 % for CHBr3) result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air–sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air–sea transfer velocity (k) parameterizations, which was performed here for eight different parameterizations. The testing of these different k values is of special interest for DMS, as recently published parameterizations derived by direct flux measurements using eddy covariance measurements suggest decreasing k values at high wind speeds or a linear relationship with wind speed. Implementing these parameterizations reduces discrepancies in modelled DMS atmospheric mixing ratios and observations by a factor of 1.5 compared to parameterizations with a quadratic or cubic relationship to wind speed.

We present the application of time-of-flight mass spectrometry (TOF MS) for the analysis of halocarbons in the atmosphere after cryogenic sample preconcentration and gas chromatographic separation. For the described field of application, the quadrupole mass spectrometer (QP MS) is a state-of-the-art detector. This work aims at comparing two commercially available instruments, a QP MS and a TOF MS, with respect to mass resolution, mass accuracy, stability of the mass axis and instrument sensitivity, detector sensitivity, measurement precision and detector linearity. Both mass spectrometers are operated on the same gas chromatographic system by splitting the column effluent to both detectors. The QP MS had to be operated in optimised single ion monitoring (SIM) mode to achieve a sensitivity which could compete with the TOF MS. The TOF MS provided full mass range information in any acquired mass spectrum without losing sensitivity. Whilst the QP MS showed the performance already achieved in earlier tests, the sensitivity of the TOF MS was on average higher than that of the QP MS in the "operational" SIM mode by a factor of up to 3, reaching detection limits of less than 0.2 pg. Measurement precision determined for the whole analytical system was up to 0.2% depending on substance and sampled volume. The TOF MS instrument used for this study displayed significant non-linearities of up to 10% for two-thirds of all analysed substances.

During the recent SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive data set of all halogen species relevant for the atmospheric budget of total organic bromine was collected in the western Pacific region using the Falcon aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully automated in situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers – coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground-based state-of-the-art GC / MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CH2BrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2σ measurement uncertainties. In contrast to the suggestion that the western Pacific could be a region of strongly increased atmospheric VSLS abundance (Pyle et al., 2011), we found only in the upper troposphere a slightly enhanced amount of total organic bromine from VSLS relative to the levels reported in Montzka and Reimann et al. (2011) for other tropical regions. From the SHIVA observations in the upper troposphere, a budget for total organic bromine, including four halons (H-1301, H-1211, H-1202, H-2402), CH3Br and the VSLS, is derived for the level of zero radiative heating (LZRH), the input region for the tropical tropopause layer (TTL) and thus also for the stratosphere. With the exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka and Reimann et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidising capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF (National Science Foundation) HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38%) to 0.78 (115%) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24%) to 1.25 (167%) ppt. We also use aircraft observations made during the 2011 Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) campaign, in the tropical western Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (BryVSLS). Our simulations show BryVSLS ranges from ~4.0 to 8.0 ppt depending on the inventory. We report an optimised estimate at the lower end of this range (~4 ppt) based on combining the CHBr3 and CH2Br2 inventories which give best agreement with the compilation of observations in the tropics.

Estimates of the recovery time of stratospheric ozone heavily rely on the exact knowledge of the processes that lead to the decomposition of the relevant halogenated source gases. Crucial parameters in this context are fractional release factors (FRFs) as well as stratospheric lifetimes and ozone depletion potentials (ODPs). We here present data from the analysis of air samples collected between 2009 and 2011 on board research aircraft flying in the mid- and high-latitude stratosphere and infer the above-mentioned parameters for ten major source gases: CFCl3 (CFC-11), CF2Cl2 (CFC-12), CF2ClCFCl2 (CFC-113), CCl4 (carbon tetrachloride), CH3CCl3 (methyl chloroform), CHF2Cl (HCFC-22), CH3CFCl2 (HCFC-141b), CH3CF2Cl (HCFC-142b), CF2ClBr (H-1211), and CF3Br (H-1301). The inferred correlations of their FRFs with mean ages of air reveal less decomposition as compared to previous studies for most compounds. When using the calculated set of FRFs to infer equivalent stratospheric chlorine, we find a reduction of more than 20% as compared to the values inferred in the most recent Scientific Assessment of Ozone Depletion by the World Meteorological Organisation (WMO, 2011). We also note that FRFs and their correlations with mean age are not generally time-independent as often assumed. The stratospheric lifetimes were calculated relative to that of CFC-11. Within our uncertainties the ratios between stratospheric lifetimes inferred here agree with the values in recent WMO reports except for CFC-11, CFC-12 and CH3CCl3. Finally, we calculate lower ODPs than recommended by WMO for six out of ten compounds, with changes most pronounced for the three HCFCs. Collectively these newly calculated values may have important implications for the severity and recovery time of stratospheric ozone loss.

We conducted measurements of the five important short-lived organic bromine species in the marine boundary layer (MBL). Measurements were made in the Northern Hemisphere mid-latitudes (Sylt Island, North Sea) in June 2009 and in the tropical Western Pacific during the TransBrom ship campaign in October 2009. For the one-week time series on Sylt Island, mean mixing ratios of CHBr3, CH2Br2, CHBr2Cl and CH2BrCl were 2.0, 1.1, 0.2, 0.1 ppt, respectively. We found maxima of 5.8 and 1.6 ppt for the two main components CHBr3 and CH2Br2. Along the cruise track in the Western Pacific (between 41° N and 13° S) we measured mean mixing ratios of 0.9, 0.9, 0.2, 0.1 and 0.1 ppt for CHBr3, CH2Br2, CHBrCl2, CHBr2Cl and CH2BrCl. Air samples with coastal influence showed considerably higher mixing ratios than the samples with open ocean origin. Correlation analyses of the two data sets yielded strong linear relationships between the mixing ratios of four of the five species (except for CH2BrCl). Using a combined data set from the two campaigns and a comparison with the results from two former studies, rough estimates of the molar emission ratios between the correlated substances were: 9/1/0.35/0.35 for CHBr3/CH2Br2/CHBrCl2/CHBr2Cl. Additional measurements were made in the tropical tropopause layer (TTL) above Teresina (Brazil, 5° S) in June 2008, using balloon-borne cryogenic whole air sampling technique. Near the level of zero clear-sky net radiative heating (LZRH) at 14.8 km about 2.25 ppt organic bromine was bound to the five short-lived species, making up 13% of total organic bromine (17.82 ppt). CH2Br2 (1.45 ppt) and CHBr3 (0.56 ppt) accounted for 90% of the budget of short-lived compounds in that region. Near the tropopause (at 17.5 km) organic bromine from these substances was reduced to 1.35 ppt, with 1.07 and 0.12 ppt attributed to CH2Br2 and CHBr3, respectively.

In this paper we present evidence that the observed increase in tropical upwelling after the year 2000 may be attributed to a change in the Brewer-Dobson circulation pattern. For this purpose, we use the concept of transit times derived from residual circulation trajectories and different in-situ measurements of ozone and nitrous dioxide. Observations from the Canadian midlatitude ozone profile record, probability density functions of in-situ N2O observations and a shift of the N2O-O3 correlation slopes, taken together, indicate that the increased upwelling in the tropics after the year 2000 appears to have triggered an intensification of tracer transport from the tropics into the extratropics in the lower stratosphere below about 500 K. This finding is corroborated by the fact that transit times along the shallow branch of the residual circulation into the LMS have decreased for the same time period (1993–2003). On a longer time scale (1979–2009), the transit time of the shallow residual circulation branch show a steady decrease of about −1 month/decade over the last 30 yr, while the transit times of the deep branch remain unchanged. This highlights that changes in the upwelling across the tropical tropopause are not sufficient as an indicator for changes in the entire Brewer-Dobson circulation.

Transport into the extratropical lowermost stratosphere (LMS) can be divided into a slow part (time-scale of several months to years) associated with the global-scale stratospheric residual circulation and a fast part (time-scale of days to a few months) associated with (mostly quasi-horizontal) mixing (i.e. two-way irreversible transport, including extratropical stratosphere-troposphere exchange). The stratospheric residual circulation may be considered to consist of two branches: a deep branch more strongly associated with planetary waves breaking in the middle to upper stratosphere, and a shallow branch associated with synoptic and planetary scale waves breaking in the subtropical lower stratosphere. In this study the contribution due to the stratospheric residual circulation alone to transport into the LMS is quantified using residual circulation trajectories, i.e. trajectories driven by the (time-dependent) residual mean meridional and vertical velocities. This contribution represents the advective part of the overall transport into the LMS and can be viewed as providing a background onto which the effect of mixing has to be added. Residual mean velocities are obtained from a comprehensive chemistry-climate model as well as from reanalysis data. Transit times of air traveling from the tropical tropopause to the LMS along the residual circulation streamfunction are evaluated and compared to recent mean age of air estimates. A time-scale separation with much smaller transit times into the mid-latitudinal LMS than into polar LMS is found that is indicative of a separation of the shallow from the deep branch of the residual circulation. This separation between the shallow and the deep circulation branch is further manifested in a distinction in the aspect ratio of the vertical to meridional extent of the trajectories, the integrated mass flux along the residual circulation trajectories, as well as the stratospheric entry latitude of the trajectories. The residual transit time distribution reproduces qualitatively the observed seasonal cycle of youngest air in the extratropical LMS in fall and oldest air in spring.

A comprehensive evaluation of seasonal backward trajectories initialized in the northern hemisphere lowermost stratosphere (LMS) has been performed to investigate the factors that determine the temporal and spatial structure of troposphere-to-stratosphere-transport (TST) and it's impact on the LMS. In particular we explain the fundamental role of the transit time since last TST (tTST) for the chemical composition of the LMS. According to our results the structure of the LMS can be characterized by a layer with tTSTtTST indicating less frequent mixing and a smaller fraction of tropospheric air. Thus the LMS constitutes a region of two well defined regimes of tropospheric influence. These can be characterized mainly by different transport times from the troposphere and different fractions of tropospheric air. Carbon monoxide (CO) mirrors this structure of tTST due to it's finite lifetime on the order of three months. Water vapour isopleths, on the other hand, do not uniquely indicate TST and are independent of tTST, but are determined by the Lagrangian Cold Point (LCP) of air parcels. Most of the backward trajectories from the LMS experienced their LCP in the tropics and sub-tropics, and TST often occurs 20 days after trajectories have encountered their LCP. Therefore, ExTL properties deduced from CO and H2O provide totally different informations on transport and particular TST for the LMS.

We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a substitute for ozone depleting compounds, in air samples originating from remote regions of the atmosphere and present evidence for its accelerating growth. Observed mixing ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the current northern mid-latitudinal upper troposphere. Firn air samples collected in Greenland were used to reconstruct a history of atmospheric abundance. Year-on-year increases were deduced, with acceleration in the growth rate from 0.029 ppt per year in 2000 to 0.056 ppt per year in 2007. Upper tropospheric air samples provide evidence for a continuing growth until late 2009. Furthermore we calculated a stratospheric lifetime of 370 years from measurements of air samples collected on board high altitude aircraft and balloons. Emission estimates were determined from the reconstructed atmospheric trend and suggest that current "bottom-up" estimates of global emissions for 2005 are too high by a factor of three.

Fractional release factors (FRFs) of organic trace gases are time-independent quantities that influence the calculation of Global Warming Potentials and Ozone Depletion Potentials. We present the first set of vertically resolved FRFs for 15 long-lived halocarbons in the tropical stratosphere up to 34 km altitude. They were calculated from measurements on air samples collected on board balloons and a high altitude aircraft. We compare the derived dependencies of FRFs on the mean stratospheric transit times (the so-called mean ages of air) with similarly derived FRFs originating from measurements at higher latitudes and find significant differences. Moreover a comparison with averaged FRFs currently used by the World Meteorological Organisation revealed the limitations of these measures due to their observed vertical and latitudinal variability. The presented data set could be used to improve future ozone level and climate projections.

The seasonality of transport and mixing of air into the lowermost stratosphere (LMS) is studied using distributions of mean age of air and a mass balance approach, based on in-situ observations of SF6 and CO2 during the SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) aircraft campaigns. Combining the information of the mean age of air and the water vapour distributions we demonstrate that the tropospheric air transported into the LMS above the extratropical tropopause layer (ExTL) originates predominantly from the tropical tropopause layer (TTL). The concept of our mass balance is based on simultaneous measurements of the two passive tracers and the assumption that transport into the LMS can be described by age spectra which are superposition of two different modes. Based on this concept we conclude that the stratospheric influence on LMS composition is strongest in April with extreme values of the tropospheric fractions (α1) below 20% and that the strongest tropospheric signatures are found in October with α1 greater than 80%. Beyond the fractions, our mass balance concept allows us to calculate the associated transit times for transport of tropospheric air from the tropics into the LMS. The shortest transit times (

The total stratospheric organic chlorine and bromine burden was derived from balloon-borne measurements in the tropics (Teresina, Brazil, 5°04´ S, 42°52´ W) in 2005. Whole air samples were collected cryogenically at altitudes between 15 and 34 km. For the first time, we report measurements of a set of 28 chlorinated and brominated substances in the tropical upper troposphere and stratosphere including ten substances with an atmospheric lifetime of less than half a year. The substances were quantified using pre-concentration techniques followed by Gas Chromatography with Mass Spectrometric detection. In the tropical tropopause layer at altitudes between 15 and 17 km we found 1.1–1.4% of the chlorine and 6–8% of the bromine to be present in the form of very short-lived organic compounds. By combining the data with tropospheric reference data and age of air observations the abundances of inorganic chlorine and bromine (Cly and Bry) were derived. At an altitude of 34 km we calculated 3062 ppt of Cly and 17.5 ppt of Bry from the decomposition of both long- and short-lived organic source gases. Furthermore we present indications for the presence of additional organic brominated substances in the tropical upper troposphere and stratosphere.

During SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) we performed measurements of a wide range of trace gases with different lifetimes and sink/source characteristics in the northern hemispheric upper troposphere (UT) and lowermost stratosphere (LMS). A large number of in-situ instruments were deployed on board a Learjet 35A, flying at altitudes up to 13.7 km, at times reaching to nearly 380 K potential temperature. Eight measurement campaigns (consisting of a total of 36 flights), distributed over all seasons and typically covering latitudes between 35° N and 75° N in the European longitude sector (10° W–20° E), were performed. Here we present an overview of the project, describing the instrumentation, the encountered meteorological situations during the campaigns and the data set available from SPURT. Measurements were obtained for N2O, CH4, CO, CO2, CFC12, H2, SF6, NO, NOy, O3 and H2O. We illustrate the strength of this new data set by showing mean distributions of the mixing ratios of selected trace gases, using a potential temperature-equivalent latitude coordinate system. The observations reveal that the LMS is most stratospheric in character during spring, with the highest mixing ratios of O3 and NOy and the lowest mixing ratios of N2O and SF6. The lowest mixing ratios of NOy and O3 are observed during autumn, together with the highest mixing ratios of N2O and SF6 indicating a strong tropospheric influence. For H2O, however, the maximum concentrations in the LMS are found during summer, suggesting unique (temperature- and convection-controlled) conditions for this molecule during transport across the tropopause. The SPURT data set is presently the most accurate and complete data set for many trace species in the LMS, and its main value is the simultaneous measurement of a suite of trace gases having different lifetimes and physical-chemical histories. It is thus very well suited for studies of atmospheric transport, for model validation, and for investigations of seasonal changes in the UT/LMS, as demonstrated in accompanying and elsewhere published studies.

During several balloon flights inside the Arctic polar vortex in early 2003, unusual trace gas distributions were observed, which indicate a strong influence of mesospheric air in the stratosphere. The tuneable diode laser (TDL) instrument SPIRALE (Spectroscopie Infra-Rouge par Absorption de Lasers Embarqués) measured unusually high CO values (up to 600 ppb) on 27 January at about 30 km altitude. The cryosampler BONBON sampled air masses with very high molecular Hydrogen, extremely low SF6 and enhanced CO values on 6 March at about 25 km altitude. Finally, the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) Fourier Transform Infra-Red (FTIR) spectrometer showed NOy values which are significantly higher than NOy* (the NOy derived from a correlation between N2O and NOy under undisturbed conditions), on 21 and 22 March in a layer centred at 22 km altitude. Thus, the mesospheric air seems to have been present in a layer descending from about 30 km in late January to 25 km altitude in early March and about 22 km altitude on 20 March. We present corroborating evidence from a model study using the KASIMA (KArlsruhe SImulation model of the Middle Atmosphere) model that also shows a layer of mesospheric air, which descended into the stratosphere in November and early December 2002, before the minor warming which occurred in late December 2002 lead to a descent of upper stratospheric air, cutting off a layer in which mesospheric air is present. This layer then descended inside the vortex over the course of the winter. The same feature is found in trajectory calculations, based on a large number of trajectories started in the vicinity of the observations on 6 March. Based on the difference between the mean age derived from SF6 (which has an irreversible mesospheric loss) and from CO2 (whose mesospheric loss is much smaller and reversible) we estimate that the fraction of mesospheric air in the layer observed on 6 March, must have been somewhere between 35% and 100%.

No abstract available.