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The transport history of tropospheric air masses above the tropical western Pacific (TWP) is reflected by the local ozone and relative humidity (RH) characteristics. In boreal winter, the TWP is the main global entry point for air masses into the stratosphere and therefore a key region of atmospheric chemistry and dynamics. Our study aims to identify air masses with different pathways to the TWP using ozone and radio soundings from Palau from 2016–2019. Supported by backward trajectory calculations, we found five different types of air masses. We further defined locally controlled ozone and RH background profiles based on monthly statistics and analyzed corresponding anomalies in the 5–10 km altitude range. Our results show a bimodality in RH anomalies. Humid and ozone-poor background air masses are of local or Pacific convective origin and occur year-round, but they dominate from August until October. Anomalously dry and ozone-rich air masses indicate a non-local origin in tropical Asia and are transported to the TWP via an anticyclonic route, mostly from February to April. The geographic location of origin suggests anthropogenic pollution or biomass burning as a cause for ozone production. We propose large-scale descent within the tropical troposphere and radiative cooling in connection with the Hadley circulation as being responsible for the dehydration during transport. The trajectory analysis revealed no indication of a stratospheric influence. Our study thus presents a valuable contribution to the discussion about anomalous layers of dry ozone-rich air observed in ozone-poor background profiles in the TWP.

The tropical western Pacific is recognized as an important region for stratosphere–troposphere exchange but lies in a data-sparse location that had a measurement gap in the global ozone sounding network. The Palau Atmospheric Observatory (PAO, approx. 7.3∘ N, 134.5∘ E) was established to study the atmospheric composition above the remote tropical western Pacific with a comprehensive instrumental setup. Since 2016, two laboratory containers in Palau host a Fourier transform infrared spectrometer; a lidar (micro-lidar until 2016, cloud and aerosol lidar from 2018); a Pandora 2S photometer; and laboratory space for weather balloon soundings with ozone, water vapor, aerosol, and radiosondes. In this analysis, we focus on the continuous, fortnightly ozone sounding program with electrochemical concentration cell (ECC) ozonesondes. The aim of this study is to introduce the PAO and its research potential, present the first observation of the typical seasonal cycle of tropospheric ozone in the tropical western Pacific based on a multiannual record of in situ observations, and investigate major drivers of variability and seasonal variation from January 2016 until December 2021​​​​​​​ related to the large-scale atmospheric circulation. We present the PAO ozone (O3) volume mixing ratios (VMR) and relative humidity (RH) time series complemented by other observations. The site is exposed to year-round high convective activity reflected in dominating low O3 VMR and high RH. In 2016, the impact of the strong El Niño is evident as a particularly dry, ozone-rich episode. The main modulator of annual tropospheric O3 variability is identified as the movement of the Intertropical Convergence Zone (ITCZ), with the lowest O3 VMR in the free troposphere during the ITCZ position north of Palau. An analysis of the relation of O3 and RH for the PAO and selected sites from the Southern Hemispheric Additional Ozonesondes (SHADOZ) network reveals three different regimes. Palau's O3 / RH distribution resembles the one in Fiji, Java and American Samoa but is unique in its seasonality and its comparably narrow Gaussian distribution around low O3 VMR and the evenly distributed RH. A previously found bimodal distribution of O3 VMR and RH could not be seen for the full Palau record but only during specific seasons and years. Due to its unique remote location, Palau is an ideal atmospheric background site to detect changes in air dynamics imprinted on the chemical composition of the tropospheric column. The efforts to establish, run and maintain the PAO have succeeded to fill an observational gap in the remote tropical western Pacific and give good prospects for ongoing operations. The ECC sonde record will be integrated into the SHADOZ database in the near future.

During the winter of 2019/2020, as the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) project started its work, the Arctic Oscillation (AO) experienced some of its largest shifts, ranging from a highly negative index in November 2019 to an extremely positive index during January–February–March (JFM) 2020. The permanent positive AO phase for the 3 months of JFM 2020 was accompanied by a prevailing positive phase of the Arctic Dipole (AD) pattern. Here we analyze the sea ice thickness (SIT) distribution based on CryoSat-2/SMOS satellite-derived data augmented with results from the hindcast simulation by the fully coupled Regional Arctic System Model (RASM) from November 2019 through March 2020. A notable result of the positive AO phase during JFM 2020 was large SIT anomalies of up to 1.3 m that emerged in the Barents Sea (BS), along the northeastern Canadian coast and in parts of the central Arctic Ocean. These anomalies appear to be driven by nonlinear interactions between thermodynamic and dynamic processes. In particular, in the Barents and Kara seas (BKS), they are a result of enhanced ice growth connected with low-temperature anomalies and the consequence of intensified atmospherically driven sea ice transport and deformations (i.e., ice divergence and shear) in this area. The Davies Strait, the east coast of Greenland and the BS regions are characterized by convergence and divergence changes connected with thinner sea ice at the ice borders along with an enhanced impact of atmospheric wind forcing. Low-pressure anomalies that developed over the eastern Arctic during JFM 2020 increased northerly winds from the cold Arctic Ocean to the BS and accelerated the southward drift of the MOSAiC ice floe. The satellite-derived and simulated sea ice velocity anomalies, which compared well during JFM 2020, indicate a strong acceleration of the Transpolar Drift relative to the mean for the past decade, with intensified speeds of up to 6 km d−1. As a consequence, sea ice transport and deformations driven by atmospheric surface wind forcing accounted for the bulk of the SIT anomalies, especially in January 2020 and February 2020. RASM intra-annual ensemble forecast simulations with 30 ensemble members forced with different atmospheric boundary conditions from 1 November 2019 through 30 April 2020 show a pronounced internal variability in the sea ice volume, driven by thermodynamic ice-growth and ice-melt processes and the impact of dynamic surface winds on sea ice formation and deformation. A comparison of the respective SIT distributions and turbulent heat fluxes during the positive AO phase in JFM 2020 and the negative AO phase in JFM 2010 corroborates the conclusion that winter sea ice conditions in the Arctic Ocean can be significantly altered by AO variability.

In September 2019, the research icebreaker Polarstern started the largest multidisciplinary Arctic expedition to date, the MOSAiC (Multidisciplinary drifting Observatory for the Study of Arctic Climate) drift experiment. Being moored to an ice floe for a whole year, thus including the winter season, the declared goal of the expedition is to better understand and quantify relevant processes within the atmosphere–ice–ocean system that impact the sea ice mass and energy budget, ultimately leading to much improved climate models. Satellite observations, atmospheric reanalysis data, and readings from a nearby meteorological station indicate that the interplay of high ice export in late winter and exceptionally high air temperatures resulted in the longest ice-free summer period since reliable instrumental records began. We show, using a Lagrangian tracking tool and a thermodynamic sea ice model, that the MOSAiC floe carrying the Central Observatory (CO) formed in a polynya event north of the New Siberian Islands at the beginning of December 2018. The results further indicate that sea ice in the vicinity of the CO ( km distance) was younger and 36 % thinner than the surrounding ice with potential consequences for ice dynamics and momentum and heat transfer between ocean and atmosphere. Sea ice surveys carried out on various reference floes in autumn 2019 verify this gradient in ice thickness, and sediments discovered in ice cores (so-called dirty sea ice) around the CO confirm contact with shallow waters in an early phase of growth, consistent with the tracking analysis. Since less and less ice from the Siberian shelves survives its first summer (Krumpen et al., 2019), the MOSAiC experiment provides the unique opportunity to study the role of sea ice as a transport medium for gases, macronutrients, iron, organic matter, sediments and pollutants from shelf areas to the central Arctic Ocean and beyond. Compared to data for the past 26 years, the sea ice encountered at the end of September 2019 can already be classified as exceptionally thin, and further predicted changes towards a seasonally ice-free ocean will likely cut off the long-range transport of ice-rafted materials by the Transpolar Drift in the future. A reduced long-range transport of sea ice would have strong implications for the redistribution of biogeochemical matter in the central Arctic Ocean, with consequences for the balance of climate-relevant trace gases, primary production and biodiversity in the Arctic Ocean.

We present a Lagrangian convective transport scheme developed for global chemistry and transport models, which considers the variable residence time that an air parcel spends in convection. This is particularly important for accurately simulating the tropospheric chemistry of short-lived species, e.g., for determining the time available for heterogeneous chemical processes on the surface of cloud droplets. In current Lagrangian convective transport schemes air parcels are stochastically redistributed within a fixed time step according to estimated probabilities for convective entrainment as well as the altitude of detrainment. We introduce a new scheme that extends this approach by modeling the variable time that an air parcel spends in convection by estimating vertical updraft velocities. Vertical updraft velocities are obtained by combining convective mass fluxes from meteorological analysis data with a parameterization of convective area fraction profiles. We implement two different parameterizations: a parameterization using an observed constant convective area fraction profile and a parameterization that uses randomly drawn profiles to allow for variability. Our scheme is driven by convective mass fluxes and detrainment rates that originate from an external convective parameterization, which can be obtained from meteorological analysis data or from general circulation models. We study the effect of allowing for a variable time that an air parcel spends in convection by performing simulations in which our scheme is implemented into the trajectory module of the ATLAS chemistry and transport model and is driven by the ECMWF ERA-Interim reanalysis data. In particular, we show that the redistribution of air parcels in our scheme conserves the vertical mass distribution and that the scheme is able to reproduce the convective mass fluxes and detrainment rates of ERA-Interim. We further show that the estimated vertical updraft velocities of our scheme are able to reproduce wind profiler measurements performed in Darwin, Australia, for velocities larger than 0.6 m s−1. SO2 is used as an example to show that there is a significant effect on species mixing ratios when modeling the time spent in convective updrafts compared to a redistribution of air parcels in a fixed time step. Furthermore, we perform long-time global trajectory simulations of radon-222 and compare with aircraft measurements of radon activity.

Stratospheric ozone loss inside the Arctic polar vortex for the winters between 2004–2005 and 2012–2013 has been quantified using measurements from the space-borne Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). For the first time, an evaluation has been performed of six different ozone loss estimation methods based on the same single observational dataset to determine the Arctic ozone loss (mixing ratio loss profiles and the partial-column ozone losses between 380 and 550 K). The methods used are the tracer-tracer correlation, the artificial tracer correlation, the average vortex profile descent, and the passive subtraction with model output from both Lagrangian and Eulerian chemical transport models (CTMs). For the tracer-tracer, the artificial tracer, and the average vortex profile descent approaches, various tracers have been used that are also measured by ACE-FTS. From these seven tracers investigated (CH4, N2O, HF, OCS, CFC-11, CFC-12, and CFC-113), we found that CH4, N2O, HF, and CFC-12 are the most suitable tracers for investigating polar stratospheric ozone depletion with ACE-FTS v3.5. The ozone loss estimates (in terms of the mixing ratio as well as total column ozone) are generally in good agreement between the different methods and among the different tracers. However, using the average vortex profile descent technique typically leads to smaller maximum losses (by approximately 15–30 DU) compared to all other methods. The passive subtraction method using output from CTMs generally results in slightly larger losses compared to the techniques that use ACE-FTS measurements only. The ozone loss computed, using both measurements and models, shows the greatest loss during the 2010–2011 Arctic winter. For that year, our results show that maximum ozone loss (2.1–2.7 ppmv) occurred at 460 K. The estimated partial-column ozone loss inside the polar vortex (between 380 and 550 K) using the different methods is 66–103, 61–95, 59–96, 41–89, and 85–122 DU for March 2005, 2007, 2008, 2010, and 2011, respectively. Ozone loss is difficult to diagnose for the Arctic winters during 2005–2006, 2008–2009, 2011–2012, and 2012–2013, because strong polar vortex disturbance or major sudden stratospheric warming events significantly perturbed the polar vortex, thereby limiting the number of measurements available for the analysis of ozone loss.

The Asian summer monsoon anticyclone (ASMA) is a major meteorological system of the upper troposphere–lower stratosphere (UTLS) during boreal summer. It is known to contain enhanced tropospheric trace gases and aerosols, due to rapid lifting from the boundary layer by deep convection and subsequent horizontal confinement. Given its dynamical structure, the ASMA represents an efficient pathway for the transport of pollutants to the global stratosphere. A detailed understanding of the thermal structure and processes in the ASMA requires accurate in situ measurements. Within the StratoClim project we performed state-of-the-art balloon-borne measurements of temperature, water vapor, ozone and aerosol backscatter from two stations on the southern slopes of the Himalayas. In total, 63 balloon soundings were conducted during two extensive monsoon-season campaigns, in August 2016 in Nainital, India (29.4° N, 79.5° E), and in July–August 2017 in Dhulikhel, Nepal (27.6° N, 85.5° E); one shorter post-monsoon campaign was also carried out in November 2016 in Nainital. These measurements provide unprecedented insights into the UTLS thermal structure, the vertical distributions of water vapor, ozone and aerosols, cirrus cloud properties and interannual variability in the ASMA. Here we provide an overview of all of the data collected during the three campaign periods, with focus on the UTLS region and the monsoon season. We analyze the vertical structure of the ASMA in terms of significant levels and layers, identified from the temperature and potential temperature lapse rates and Lagrangian backward trajectories, which provides a framework for relating the measurements to local thermodynamic properties and the large-scale anticyclonic flow. Both the monsoon-season campaigns show evidence of deep convection and confinement extending up to 1.5–2 km above the cold-point tropopause (CPT), yielding a body of air with high water vapor and low ozone which is prone to being lifted further and mixed into the free stratosphere. Enhanced aerosol backscatter also reveals the signature of the Asian tropopause aerosol layer (ATAL) over the same region of altitudes. The Dhulikhel 2017 campaign was characterized by a 5 K colder CPT on average than in Nainital 2016 and a local water vapor maximum in the confined lower stratosphere, about 1 km above the CPT. Data assessment and modeling studies are currently ongoing with the aim of fully exploring this dataset and its implications with respect to stratospheric moistening via the ASMA system and related processes.

The Extrapolar SWIFT model is a fast ozone chemistry scheme for interactive calculation of the extrapolar stratospheric ozone layer in coupled general circulation models (GCMs). In contrast to the widely used prescribed ozone, the SWIFT ozone layer interacts with the model dynamics and can respond to atmospheric variability or climatological trends.The Extrapolar SWIFT model employs a repro-modelling approach, in which algebraic functions are used to approximate the numerical output of a full stratospheric chemistry and transport model (ATLAS). The full model solves a coupled chemical differential equation system with 55 initial and boundary conditions (mixing ratio of various chemical species and atmospheric parameters). Hence the rate of change of ozone over 24 h is a function of 55 variables. Using covariances between these variables, we can find linear combinations in order to reduce the parameter space to the following nine basic variables: latitude, pressure altitude, temperature, overhead ozone column and the mixing ratio of ozone and of the ozone-depleting families (Cly, Bry, NOy and HOy). We will show that these nine variables are sufficient to characterize the rate of change of ozone. An automated procedure fits a polynomial function of fourth degree to the rate of change of ozone obtained from several simulations with the ATLAS model. One polynomial function is determined per month, which yields the rate of change of ozone over 24 h. A key aspect for the robustness of the Extrapolar SWIFT model is to include a wide range of stratospheric variability in the numerical output of the ATLAS model, also covering atmospheric states that will occur in a future climate (e.g. temperature and meridional circulation changes or reduction of stratospheric chlorine loading).For validation purposes, the Extrapolar SWIFT model has been integrated into the ATLAS model, replacing the full stratospheric chemistry scheme. Simulations with SWIFT in ATLAS have proven that the systematic error is small and does not accumulate during the course of a simulation. In the context of a 10-year simulation, the ozone layer simulated by SWIFT shows a stable annual cycle, with inter-annual variations comparable to the ATLAS model. The application of Extrapolar SWIFT requires the evaluation of polynomial functions with 30–100 terms. Computers can currently calculate such polynomial functions at thousands of model grid points in seconds. SWIFT provides the desired numerical efficiency and computes the ozone layer 104 times faster than the chemistry scheme in the ATLAS CTM.

We present a quantitative analysis of the chemical reactions involved in polar ozone depletion in the stratosphere and of the relevant reaction pathways and cycles. While the reactions involved in polar ozone depletion are well known, quantitative estimates of the importance of individual reactions or reaction cycles are rare. In particular, there is no comprehensive and quantitative study of the reaction rates and cycles averaged over the polar vortex under conditions of heterogeneous chemistry so far. We show time series of reaction rates averaged over the core of the polar vortex in winter and spring for all relevant reactions and indicate which reaction pathways and cycles are responsible for the vortex-averaged net change of the key species involved in ozone depletion, i.e., ozone, chlorine species (ClOx, HCl, ClONO2), bromine species, nitrogen species (HNO3, NOx) and hydrogen species (HOx). For clarity, we focus on one Arctic winter (2004–2005) and one Antarctic winter (2006) in a layer in the lower stratosphere around 54 hPa and show results for additional pressure levels and winters in the Supplement. Mixing ratios and reaction rates are obtained from runs of the ATLAS Lagrangian chemistry and transport model (CTM) driven by the European Centre for Medium-Range Weather Forecasts (ECMWF) ERA-Interim reanalysis data. An emphasis is put on the partitioning of the relevant chemical families (nitrogen, hydrogen, chlorine, bromine and odd oxygen) and activation and deactivation of chlorine.

The Polar SWIFT model is a fast scheme for calculating the chemistry of stratospheric ozone depletion in polar winter. It is intended for use in global climate models (GCMs) and Earth system models (ESMs) to enable the simulation of mutual interactions between the ozone layer and climate. To date, climate models often use prescribed ozone fields, since a full stratospheric chemistry scheme is computationally very expensive. Polar SWIFT is based on a set of coupled differential equations, which simulate the polar vortex-averaged mixing ratios of the key species involved in polar ozone depletion on a given vertical level. These species are O3, chemically active chlorine (ClOx), HCl, ClONO2 and HNO3. The only external input parameters that drive the model are the fraction of the polar vortex in sunlight and the fraction of the polar vortex below the temperatures necessary for the formation of polar stratospheric clouds. Here, we present an update of the Polar SWIFT model introducing several improvements over the original model formulation. In particular, the model is now trained on vortex-averaged reaction rates of the ATLAS Chemistry and Transport Model, which enables a detailed look at individual processes and an independent validation of the different parameterizations contained in the differential equations. The training of the original Polar SWIFT model was based on fitting complete model runs to satellite observations and did not allow for this. A revised formulation of the system of differential equations is developed, which closely fits vortex-averaged reaction rates from ATLAS that represent the main chemical processes influencing ozone. In addition, a parameterization for the HNO3 change by denitrification is included. The rates of change of the concentrations of the chemical species of the Polar SWIFT model are purely chemical rates of change in the new version, whereas in the original Polar SWIFT model, they included a transport effect caused by the original training on satellite data. Hence, the new version allows for an implementation into climate models in combination with an existing stratospheric transport scheme. Finally, the model is now formulated on several vertical levels encompassing the vertical range in which polar ozone depletion is observed. The results of the Polar SWIFT model are validated with independent Microwave Limb Sounder (MLS) satellite observations and output from the original detailed chemistry model of ATLAS.

We examined observations of polar stratospheric clouds (PSCs) by CALIPSO, and of HCl and ClO by MLS along air mass trajectories, to investigate the dependence of the inferred PSC composition on the temperature history of the air parcels and the dependence of the level of chlorine activation on PSC composition. Several case studies based on individual trajectories from the Arctic winter 2009/2010 were conducted, with the trajectories chosen such that the first processing of the air mass by PSCs in this winter occurred on the trajectory. Transitions of PSC composition classes were observed to be highly dependent on the temperature history. In cases of a gradual temperature decrease, nitric acid trihydrate (NAT) and super-cooled ternary solution (STS) mixture clouds were observed. In cases of rapid temperature decrease, STS clouds were first observed, followed by NAT/STS mixture clouds. When temperatures dropped below the frost point, ice clouds formed and then transformed into NAT/STS mixture clouds when temperature increased above the frost point. The threshold temperature for rapid chlorine activation on PSCs is approximately 4 K below the NAT existence temperature, TNAT. Furthermore, simulations of the ATLAS chemistry and transport box model along the trajectories were used to corroborate the measurements and show good agreement with the observations. Rapid chlorine activation was observed when an air mass encountered PSCs. Usually, chlorine activation was limited by the amount of available ClONO2. Where ClONO2 was not the limiting factor, a large dependence on temperature was evident.

We present ozone measurements made using state-of-the-art ultraviolet photometers onboard three long-duration stratospheric balloons launched as part of the Concordiasi campaign in austral spring 2010. Ozone loss rates calculated by matching air parcels sampled at different times and places during the polar spring are in agreement with rates previously derived from ozonesonde measurements, for the vortex average, ranging between 2 and 7 ppbv per sunlit hour or between 25 and 110 ppbv per day. However, the geographical coverage of these long-duration stratospheric balloon platforms provides new insights into the temporal and spatial patterns of ozone loss over Antarctica. Very large ozone loss rates of up to 230 ppbv per day (16 ppbv per sunlit hour) are observed for air masses that are downwind of the Antarctic Peninsula and/or over the East Antarctic region. The ozone loss rate maximum downstream of the Antarctic Peninsula region is consistent with high PSC occurrence from CALIPSO and large ClO abundances from MLS satellite observations for 12–22 September 2010, and with a chemical box model simulation using JPL 2011 kinetics with full chlorine activation.

This study focuses on the question whether heat treated sewage sludge ashes are more favourable as fertilizers than untreated sewage sludge ashes (USSA) and whether their fertilization effects are comparable with commercial triple superphosphate (TSP). In a pot experiment, maize was fertilized either with one of three heat treated and Na-, Ca- and Si-compounds amended sewage sludge ashes (two glown phosphates, steel mill slag + sewage sludge ash) or USSA or TSP as control. Fertilization with USSA did not increase the biomass yield and the P uptake of maize in comparison to the P0 treatment (7.25 resp. 8.35 g dry matter/pot). Fertilization with heat treated sewage sludge ashes and TSP resulted in significantly higher yields and plant P uptakes which are on average eight times higher than treatment with USSA and P0 control. Biomass yields and P uptake of maize after fertilization with heat treated sewage sludge ashes are not significantly different from those after TSP fertilization. The main P compound in USSA is Ca3(PO4)2. By heat treatment and amendment with different sodium, calcium, sulphur and silicon containing additives or steel mill converter slag, Ca3(PO4)2 is converted to Ca- and Na-silico-phosphates, which have a higher water solubility than Ca3(PO4)2. This increased solubility is responsible for the high plant availability of this phosphates.

An extremely fast model to estimate the degree of stratospheric ozone depletion during polar winters is described. It is based on a set of coupled differential equations that simulate the seasonal evolution of vortex-averaged hydrogen chloride (HCl), nitric acid (HNO3), chlorine nitrate (ClONO2), active forms of chlorine (ClOx = Cl + ClO + 2 ClOOCl) and ozone (O3) on isentropic levels within the polar vortices. Terms in these equations account for the chemical and physical processes driving the time rate of change of these species. Eight empirical fit coefficients associated with these terms are derived by iteratively fitting the equations to vortex-averaged satellite-based measurements of HCl, HNO3 and ClONO2 and observationally derived ozone loss rates. The system of differential equations is not stiff and can be solved with a time step of one day, allowing many years to be processed per second on a standard PC. The inputs required are the daily fractions of the vortex area covered by polar stratospheric clouds and the fractions of the vortex area exposed to sunlight. The resultant model, SWIFT (Semi-empirical Weighted Iterative Fit Technique), provides a fast yet accurate method to simulate ozone loss rates in polar regions. SWIFT's capabilities are demonstrated by comparing measured and modeled total ozone loss outside of the training period.

Most of the short-lived biogenic and anthropogenic chemical species that are emitted into the atmosphere break down efficiently by reaction with OH and do not reach the stratosphere. Here we show the existence of a pronounced minimum in the tropospheric column of ozone over the West Pacific, the main source region for stratospheric air, and suggest a corresponding minimum of the tropospheric column of OH. This has the potential to amplify the impact of surface emissions on the stratospheric composition compared to the impact when assuming globally uniform OH conditions. Specifically, the role of emissions of biogenic halogenated species for the stratospheric halogen budget and the role of increasing emissions of SO2 in Southeast Asia or from minor volcanic eruptions for the increasing stratospheric aerosol loading need to be reassessed in light of these findings. This is also important since climate change will further modify OH abundances and emissions of halogenated species. Our study is based on ozone sonde measurements carried out during the TransBrom cruise with the RV Sonne roughly along 140–150° E in October 2009 and corroborating ozone and OH measurements from satellites, aircraft campaigns and FTIR instruments. Model calculations with the GEOS-Chem Chemistry and Transport Model (CTM) and the ATLAS CTM are used to simulate the tropospheric OH distribution over the West Pacific and the transport pathways to the stratosphere. The potential effect of the OH minimum on species transported into the stratosphere is shown via modeling the transport and chemistry of CH2Br2 and SO2.

The international research project RECONCILE has addressed central questions regarding polar ozone depletion, with the objective to quantify some of the most relevant yet still uncertain physical and chemical processes and thereby improve prognostic modelling capabilities to realistically predict the response of the ozone layer to climate change. This overview paper outlines the scope and the general approach of RECONCILE, and it provides a summary of observations and modelling in 2010 and 2011 that have generated an in many respects unprecedented dataset to study processes in the Arctic winter stratosphere. Principally, it summarises important outcomes of RECONCILE including (i) better constraints and enhanced consistency on the set of parameters governing catalytic ozone destruction cycles, (ii) a better understanding of the role of cold binary aerosols in heterogeneous chlorine activation, (iii) an improved scheme of polar stratospheric cloud (PSC) processes that includes heterogeneous nucleation of nitric acid trihydrate (NAT) and ice on non-volatile background aerosol leading to better model parameterisations with respect to denitrification, and (iv) long transient simulations with a chemistry-climate model (CCM) updated based on the results of RECONCILE that better reproduce past ozone trends in Antarctica and are deemed to produce more reliable predictions of future ozone trends. The process studies and the global simulations conducted in RECONCILE show that in the Arctic, ozone depletion uncertainties in the chemical and microphysical processes are now clearly smaller than the sensitivity to dynamic variability.

Stratospheric chemistry and denitrification are simulated for the Arctic winter 2009/2010 with the Lagrangian Chemistry and Transport Model ATLAS. A number of sensitivity runs is used to explore the impact of uncertainties in chlorine activation and denitrification on the model results. In particular, the efficiency of chlorine activation on different types of liquid aerosol versus activation on nitric acid trihydrate clouds is examined. Additionally, the impact of changes in reaction rate coefficients, in the particle number density of polar stratospheric clouds, in supersaturation, temperature or the extent of denitrification is investigated. Results are compared to satellite measurements of MLS and ACE-FTS and to in-situ measurements onboard the Geophysica aircraft during the RECONCILE measurement campaign. It is shown that even large changes in the underlying assumptions have only a small impact on the modelled ozone loss, even though they can cause considerable differences in chemical evolution of other species and in denitrification. Differences in column ozone between the sensitivity runs stay below 10% at the end of the winter. Chlorine activation on liquid aerosols alone is able to explain the observed magnitude and morphology of the mixing ratios of active chlorine, reservoir gases and ozone. This is even true for binary aerosols (no uptake of HNO3 from the gas-phase allowed in the model). Differences in chlorine activation between sensitivity runs are within 30%. Current estimates of nitric acid trihydrate (NAT) number density and supersaturation imply that, at least for this winter, NAT clouds play a relatively small role compared to liquid clouds in chlorine activation. The change between different reaction rate coefficients for liquid or solid clouds has only a minor impact on ozone loss and chlorine activation in our sensitivity runs.

Two semi-empirical models were developed for the Antarctic stratosphere to relate the shift of species within total chlorine (Cly = HCl + ClONO2 + HOCl + 2 × Cl2 + 2×Cl2O2 + ClO + Cl) into the active forms (here: ClOx = 2×Cl2O2 + ClO), and to relate the rate of ozone destruction to ClOx. These two models provide a fast and computationally inexpensive way to describe the inter- and intra-annual evolution of ClOx and ozone mass deficit (OMD) in the Antarctic spring. The models are based on the underlying physics/chemistry of the system and capture the key chemical and physical processes in the Antarctic stratosphere that determine the interaction between climate change and Antarctic ozone depletion. They were developed considering bulk effects of chemical mechanisms for the duration of the Antarctic vortex period and quantities averaged over the vortex area. The model equations were regressed against observations of daytime ClO and OMD providing a set of empirical fit coefficients. Both semi-empirical models are able to explain much of the intra- and inter-annual variability observed in daily ClOx and OMD time series. This proof-of-concept paper outlines the semi-empirical approach to describing the evolution of Antarctic chlorine activation and ozone depletion.

In spring 2011, the Arctic polar vortex was stronger than in any other year on record. As the polar vortex started to break up in April, ozone and NO2 columns were measured with UV-visible spectrometers above the Polar Environment Atmospheric Research Laboratory (PEARL) in Eureka, Canada (80.05° N, 86.42° W) using the differential optical absorption spectroscopy (DOAS) technique. These ground-based column measurements were complemented by Ozone Monitoring Instrument (OMI) and Optical Spectrograph and Infra-Red Imager System (OSIRIS) satellite measurements, Global Modeling Initiative (GMI) simulations, and meteorological quantities. On 8 April 2011, NO2 columns above PEARL from the DOAS, OMI, and GMI datasets were approximately twice as large as in previous years. On this day, temperatures and ozone volume mixing ratios above Eureka were high, suggesting enhanced chemical production of NO2 from NO. Additionally, GMI NOx (NO + NO2) and N2O fields suggest that downward transport along the vortex edge and horizontal transport from lower latitudes also contributed to the enhanced NO2. The anticyclone that transported lower-latitude NOx above PEARL became frozen-in and persisted in dynamical and GMI N2O fields until the end of the measurement period on 31 May 2011. Ozone isolated within this frozen-in anticyclone (FrIAC) in the middle stratosphere was lost due to reactions with the enhanced NOx. Below the FrIAC (from the tropopause to 700 K), NOx driven ozone loss above Eureka was larger than in previous years, according to GMI monthly average ozone loss rates. Using the passive tracer technique, with passive ozone profiles from the Lagrangian Chemistry and Transport Model, ATLAS, ozone losses since 1 December 2010 were calculated at 600 K. In the air mass that was above Eureka on 20 May 2011, ozone losses reached 4.2 parts per million by volume (ppmv) (58%) and 4.4 ppmv (61%), when calculated using GMI and OSIRIS ozone profiles, respectively. This gas-phase ozone loss led to a more rapid decrease in ozone column amounts above Eureka in April/May 2011 compared with previous years. Ground-based, OMI, and GMI ozone total columns all decreased by more than 100 DU from 15 April to 20 May. Two lows in the ozone columns were also investigated and were attributed to a vortex remnant passing above Eureka at ~500 K on 12/13 May and an ozone mini-hole on 22/23 May.

Early winter ozone mixing ratios in the Arctic middle stratosphere show an interannual variability of about 10%. We show that ozone variability in early January is caused by dynamical processes during Arctic polar vortex formation in autumn (September to December). Observational data from satellites and ozone sondes are used in conjunction with simulations of the chemistry and transport model ATLAS to examine the relationship between the meridional and vertical origin of air enclosed in the polar vortex and its ozone amount. For this, we use a set of artificial model tracers to deduce the origin of the air masses in the vortex in January in latitude and altitude in September. High vortex mean ozone mixing ratios are correlated with a high fraction of air from low latitudes enclosed in the vortex and a high fraction of air that experienced small net subsidence (in a Lagrangian sense). As a measure for the strength of the Brewer-Dobson circulation and meridional mixing in autumn, we use the Eliassen-Palm flux through the mid-latitude tropopause averaged from September to November. In the lower stratosphere, this quantity correlates well with the origin of air enclosed in the vortex and reasonably well with the ozone amount in early winter.

Dynamical processes during the formation phase of the Arctic stratospheric vortex in autumn (from September to December) can introduce considerable interannual variability in the amount of ozone that is incorporated into the vortex. Chemistry in autumn tends to remove part of this variability because ozone relaxes towards equilibrium. As a quantitative measure of how important dynamical variability during vortex formation is for the winter ozone abundances above the Arctic we analyze which fraction of an ozone anomaly induced during vortex formation persists until early winter (3 January). The work is based on the Lagrangian Chemistry Transport Model ATLAS. In a case study, model runs for the winter 1999–2000 are used to assess the fate of an ozone anomaly artificially introduced during the vortex formation phase on 16 September. In addition, runs with reduced resolution explore the sensitivity of the results to interannual changes in transport, mixing, temperatures and NOx. The runs provide information about the persistence of the induced ozone anomaly as a function of time, potential temperature and latitude. The induced ozone anomaly survives longer inside the polar vortex than outside the vortex. Half of the initial perturbation survives until 3 January at 550 K inside the polar vortex, with a rapid fall off towards higher levels, mainly due to NOx induced chemistry. Above 750 K the signal falls to values below 0.5%. Hence, dynamically induced ozone variability from the early vortex formation phase cannot significantly contribute to early winter variability above 750 K. At lower levels increasingly larger fractions of the initial perturbation survive, reaching 90% at 450 K. In this vertical range dynamical processes during the vortex formation phase are crucial for the ozone abundance in early winter.

The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer) JClOOCl is a critical parameter in catalytic cycles destroying ozone (O3) in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm), significant discrepancies between laboratory measurements of ClOOCl absorption cross sections and spectra cause a large uncertainty in JClOOCl. Previous investigations of the consistency of published JClOOCl with atmospheric observations of chlorine monoxide (ClO) and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the ClOOCl formation rate constant krec. Here, we constrain the atmospherically effective JClOOCl independent of krec, using ClO measured in the same air masses before and directly after sunrise during an aircraft flight that was part of the RECONCILE field campaign in the winter 2010 from Kiruna, Sweden. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the increase in ClO concentrations is significantly faster than expected from JClOOCl based on the absorption spectrum proposed by Pope et al. (2007), but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009). In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm is not supported by our observations. The observed night-time ClO would not be consistent with a ClO/ClOOCl thermal equilibrium constant significantly higher than the one proposed by Plenge et al. (2005).

Carbon monoxide (CO) and ozone (O3) have been measured in the Western Pacific (43° N to 35° S) during a ship campaign with Research Vessel Sonne in fall 2009. Observations have been performed using ship-based solar absorption Fourier Transform infrared spectrometry, flask sampling, balloon sounding, and in-situ Fourier Transform infrared analysis. The results obtained are compared to the GEOS-Chem global 3-D chemistry transport model for atmospheric composition. In general, a very good agreement is found between the GEOS-Chem model and all instruments. The CO and O3 distributions show a comparable variability suggesting an impact from the same source regions. Tagged-CO simulations implemented in the GEOS-Chem model make it possible to differentiate between different source processes and source regions. The source regions are verified with HYSPLIT backward trajectory calculations. In the Northern Hemisphere fossil fuel combustion in Asia is the dominant source. European and North American fossil fuel combustion also contribute to Northern Hemispheric CO pollution. In the Southern Hemisphere contributions from biomass burning and fossil fuel combustion are dominant; African biomass burning has a significant impact on Western Pacific CO pollution. Furthermore, in the tropical Western Pacific enhanced upper tropospheric CO within the tropical tropopause layer mainly originates from Indonesian fossil fuel combustion and can be transported into the stratosphere. The source regions of the measured O3 pollution are simulated with a tagged-O3 simulation implemented in the GEOS-Chem model. Similar source regions compared to the tagged-CO simulations are identified by the model. In the Northern Hemisphere contributions from Asia, Europe, and North America are significant. In the Southern Hemisphere emissions from South America, south-east Africa, and Oceania significantly contribute to the measured O3 pollution.

Key kinetic parameters governing the partitioning of chlorine species in the Antarctic polar stratosphere were retrieved from 28 days of chlorine monoxide (ClO) microwave radiometer measurements made during the late winter/early spring of 2005 at Scott Base (77.85° S, 166.75° E). During day-time the loss of the ClO dimer chlorine peroxide (ClOOCl) occurs mainly by photolysis. Some time after sunrise, a photochemical equilibrium is established and the ClO/ClOOCl partitioning is determined by the ratio of the photolysis frequency, J, and the dimer formation rate, kf. The values of J and kf from laboratory studies remain uncertain to a considerable extent, and as a complement to these ongoing studies, the goal of this work is to provide a constraint on that uncertainty based on observations of ClO profiles in the Antarctic. First an optimal estimation technique was used to derive J/kf ratios for a range of Keq values. The optimal estimation forward model was a photochemical box model that takes J, kf, and Keq as inputs, together with a priori profiles of activated chlorine (ClOx = ClO+2×ClOOCl), profiles of ozone, temperature, and pressure. JPL06 kinetics are used as a priori in the optimal estimation and for all other chemistry in the forward model. Using the more recent JPL09 kinetics results in insignificant differences in the retrieved value of J/kf. A complementary approach was used to derive the optimal kinetic parameters; the full parameter space of J, kf, Keq and ClOx was sampled to find the minimum in differences between measured and modelled ClO profiles. Furthermore, values of Keq up to 2.0 times larger than recommended by JPL06 were explored to test the sensitivity of the J/kf ratio to changes in Keq. The results show that the retrieved J/kf ratios bracket the range of 1.23 to 1.97 times the J/kf value recommended by JPL06 over the range of Keq values considered. The retrieved J/kf ratios lie in the lower half of the large uncertainty range of J/kf recommended by JPL06 and towards the upper portion of the smaller uncertainty range recommended by JPL09.

We evaluate the sensitivity of Bry entering the stratosphere with a simplified model that allows calculations over a wide parameter range for parameters that are currently poorly quantified. The model examines the transport process uncertainties in the source concentrations and lifetimes, in the convective parameterization and in the inorganic bromine washout process due to dehydration. Source concentrations at the surface and lifetimes were found to have a slight effect on the resultant Bry (1 ppt), however this was highly dependent upon, with increasing significance, the BL component of convectively delivered air. Efficiency of convective delivery of boundary layer (BL) air to the tropical tropopause layer (TTL) along with washout at the CPT were found to substantially affect Bry at 400 K – altering the delivered Bry by 3.3 ppt and 2.9 ppt, respectively. We find that the results critically depend on free tropospheric bromine source gas concentrations due to dilution of convective updrafts, and the processes that control free tropospheric bromine source gas concentrations require further attention.

ATLAS is a new global Lagrangian Chemistry and Transport Model (CTM), which includes a stratospheric chemistry scheme with 46 active species, 171 reactions, heterogeneous chemistry on polar stratospheric clouds and a Lagrangian denitrification module. Lagrangian (trajectory-based) models have several important advantages over conventional Eulerian models, including the absence of spurious numerical diffusion, efficient code parallelization and no limitation of the largest time step by the Courant-Friedrichs-Lewy criterion. This work describes and validates the stratospheric chemistry scheme of the model. Stratospheric chemistry is simulated with ATLAS for the Arctic winter 1999/2000, with a focus on polar ozone depletion and denitrification. The simulations are used to validate the chemistry module in comparison with measurements of the SOLVE/THESEO 2000 campaign. A Lagrangian denitrification module, which is based on the simulation of the nucleation, sedimentation and growth of a large number of polar stratospheric cloud particles, is used to model the substantial denitrification that occured in this winter.

The empirical relationship found between column-integrated Arctic ozone loss and the potential volume of polar stratospheric clouds inferred from meteorological analyses is recalculated in a self-consistent manner using the ERA Interim reanalyses. The relationship is found to hold at different altitudes as well as in the column. The use of a PSC formation threshold based on temperature dependent cold aerosol formation makes little difference to the original, empirical relationship. Analysis of the photochemistry leading to the ozone loss shows that activation is limited by the photolysis of nitric acid. This step produces nitrogen dioxide which is converted to chlorine nitrate which in turn reacts with hydrogen chloride on any polar stratospheric clouds to form active chlorine. The rate-limiting step is the photolysis of nitric acid: this occurs at the same rate every year and so the interannual variation in the ozone loss is caused by the extent and persistence of the polar stratospheric clouds. In early spring the ozone loss rate increases as the solar insolation increases the photolysis of the chlorine monoxide dimer in the near ultraviolet. However the length of the ozone loss period is determined by the photolysis of nitric acid which also occurs in the near ultraviolet. As a result of these compensating effects, the amount of the ozone loss is principally limited by the extent of original activation rather than its timing. In addition a number of factors, including the vertical changes in pressure and total inorganic chlorine as well as denitrification and renitrification, offset each other. As a result the extent of original activation is the most important factor influencing ozone loss. These results indicate that relatively simple parameterisations of Arctic ozone loss could be developed for use in coupled chemistry climate models.

The impact and significance of uncertainties in model calculations of stratospheric ozone loss resulting from known uncertainty in chemical kinetics parameters is evaluated in trajectory chemistry simulations for the Antarctic and Arctic polar vortices. The uncertainty in modeled ozone loss is derived from Monte Carlo scenario simulations varying the kinetic (reaction and photolysis rate) parameters within their estimated uncertainty bounds. Simulations of a typical winter/spring Antarctic vortex scenario and Match scenarios in the Arctic produce large uncertainty in ozone loss rates and integrated seasonal loss. The simulations clearly indicate that the dominant source of model uncertainty in polar ozone loss is uncertainty in the Cl2O2 photolysis reaction, which arises from uncertainty in laboratory-measured molecular cross sections at atmospherically important wavelengths. This estimated uncertainty in JCl2O2 from laboratory measurements seriously hinders our ability to model polar ozone loss within useful quantitative error limits. Atmospheric observations, however, suggest that the Cl2O2 photolysis uncertainty may be less than that derived from the lab data. Comparisons to Match, South Pole ozonesonde, and Aura Microwave Limb Sounder (MLS) data all show that the nominal recommended rate simulations agree with data within uncertainties when the Cl2O2 photolysis error is reduced by a factor of two, in line with previous in situ ClOx measurements. Comparisons to simulations using recent cross sections from Pope et al. (2007) are outside the constrained error bounds in each case. Other reactions producing significant sensitivity in polar ozone loss include BrO + ClO and its branching ratios. These uncertainties challenge our confidence in modeling polar ozone depletion and projecting future changes in response to changing halogen emissions and climate. Further laboratory, theoretical, and possibly atmospheric studies are needed.

We present a new global Chemical Transport Model (CTM) with full stratospheric chemistry and Lagrangian transport and mixing called ATLAS (Alfred Wegener InsTitute LAgrangian Chemistry/Transport System). Lagrangian (trajectory-based) models have several important advantages over conventional Eulerian (grid-based) models, including the absence of spurious numerical diffusion, efficient code parallelization and no limitation of the largest time step by the Courant-Friedrichs-Lewy criterion. The basic concept of transport and mixing is similar to the approach in the commonly used CLaMS model. Several aspects of the model are different from CLaMS and are introduced and validated here, including a different mixing algorithm for lower resolutions which is less diffusive and agrees better with observations with the same mixing parameters. In addition, values for the vertical and horizontal stratospheric bulk diffusion coefficients are inferred and compared to other studies. This work focusses on the description of the dynamical part of the model and the validation of the mixing algorithm. The chemistry module, which contains 49 species, 170 reactions and a detailed treatment of heterogeneous chemistry, will be presented in a separate paper.

For the first time the long-term interannual and spatial variability of residence time (τ) is presented for the TTL between 360 K and 400 K potential temperature (~14 to 18 km altitude). The analysis is based on a Lagrangian approach using offline calculated diabatic heating rates as vertical velocities, covering Northern Hemisphere (NH) winters from 1962–2004. The residence time τLCP–400 K, being the duration time of air parcels in the layer between the Lagrangian Cold Point (LCP) and 400 K, varies spatially and is longer (>50 days) over the maritime continent as the LCP is lowest there (

A number of field-campaigns in the tropics have been conducted in recent years with two different LIDAR systems at Paramaribo (5.8° N, 55.2° W), Suriname. The lidars detect particles in the atmosphere with high vertical and temporal resolution and are capable of detecting extremely thin cloud layers which frequently occur in the tropical tropopause layer (TTL). Radiosonde as well as operational ECMWF analysis showed that equatorial Kelvin waves propagated in the TTL and greatly modulated its temperature structure. We found a clear correlation between the temperature anomalies introduced by these waves and the occurrence of thin cirrus in the TTL. In particular we found that extremely thin ice clouds form regularly where cold anomalies shift the tropopause to high altitudes. These findings suggest an influence of Kelvin wave activity on the dehydration in the TTL and thus on the global stratospheric water vapour concentration.

The EU CANDIDOZ project investigated the chemical and dynamical influences on decadal ozone trends focusing on the Northern Hemisphere. High quality long-term ozone data sets, satellite-based as well as ground-based, and the long-term meteorological reanalyses from ECMWF and NCEP are used together with advanced multiple regression models and atmospheric models to assess the relative roles of chemistry and transport in stratospheric ozone changes. This overall synthesis of the individual analyses in CANDIDOZ shows clearly one common feature in the NH mid latitudes and in the Arctic: an almost monotonic negative trend from the late 1970s to the mid 1990s followed by an increase. In most trend studies, the Equivalent Effective Stratospheric Chlorine (EESC) which peaked in 1997 as a consequence of the Montreal Protocol was observed to describe ozone loss better than a simple linear trend. Furthermore, all individual analyses point to changes in dynamical drivers, such as the residual circulation (responsible for the meridional transport of ozone into middle and high latitudes) playing a key role in the observed turnaround. The changes in ozone transport are associated with variations in polar chemical ozone loss via heterogeneous ozone chemistry on PSCs (polar stratospheric clouds). Synoptic scale processes as represented by the new equivalent latitude proxy, by conventional tropopause altitude or by 250 hPa geopotential height have also been successfully linked to the recent ozone increases in the lowermost stratosphere. These show significant regional variation with a large impact over Europe and seem to be linked to changes in tropospheric climate patterns such as the North Atlantic Oscillation. Some influence in recent ozone increases was also attributed to the rise in solar cycle number 23. Changes from the late 1970s to the mid 1990s were found in a number of characteristics of the Arctic vortex. However, only one trend was found when more recent years are also considered, namely the tendency for cold winters to become colder.

A long-term climatology of air mass transport through the tropical tropopause layer (TTL) is presented, covering the period from 1962–2005. The transport through the TTL is calculated with a Lagrangian approach using radiative heating rates as vertical velocities in an isentropic trajectory model. We demonstrate the improved performance of such an approach compared to previous studies using vertical winds from meteorological analyses. Within the upper part of the TTL, the averaged diabatic ascent is 0.5 K/day during Northern Hemisphere (NH) winters 1992–2001. Climatological maps show a cooling and strengthening of this part of the residual circulation during the 1990s and early 2000s compared to the long-term mean. Lagrangian cold point (LCP) fields show systematic differences for varying time periods and natural forcing components. The interannual variability of LCP temperature and density fields is found to be influenced by volcanic eruptions, El Niño Southern Oscillation (ENSO), Quasi-Biennial Oscillation (QBO) and the solar cycle. The coldest and driest TTL is reached during QBO easterly phase and La Niña over the western Pacific, whereas during volcanic eruptions, El Niño and QBO westerly phase it is warmer and less dry.

Stratospheric vertical winds from analysis data in pressure (p) or hybrid pressure (σ-p) coordinates, for use in e.g. chemical transport models (CTMs) or trajectory models, often suffer both from excessive noise and errors in their mean magnitude, which in turn can introduce errors in important dynamical quantities like vertical mixing or constituent transport with the residual circulation. Since vertical velocities cannot be measured directly, they are inferred from other quantities, typically from horizontal wind divergence, that is the mass continuity equation. We propose a method to calculate the vertical wind field from the thermodynamic energy equation in p or σ-p vertical coordinates that substantially reduces noise and overestimation of the residual circulation. It is completely equivalent to the approach using potential temperature (θ) as a vertical coordinate and diabatic heating rates as vertical velocities, which has already been demonstrated to give superior results to the continuity equation. It provides a quickly realizable improvement of the vertical winds, when a change of the vertical variable would cause an inadequate effort (e.g. in CTMs). The method is only applicable for stably stratified regions like the stratosphere.

Global total ozone measurements from various satellite instruments such as SBUV, TOMS, and GOME show an increase in zonal mean total ozone at northern hemispheric (NH) mid to high latitudes since the mid-nineties. This increase could be expected from the peaking and start of decline in the effective stratospheric halogen loading, but the rather rapid increase observed in NH zonal mean total ozone suggests that another physical mechanism such as winter planetary wave activity has increased which has led to higher stratospheric Arctic temperatures. This has enhanced ozone transport into higher latitudes in recent years as part of the residual circulation and at the same time reduced the frequency of cold Arctic winters with enhanced polar ozone loss. Results from various multi-variate linear regression analyses using SBUV V8 total ozone with explanatory variables such as a linear trend or, alternatively, EESC (equivalent effective stratospheric chlorine) and on the other hand planetary wave driving (eddy heat flux) or, alternatively, polar ozone loss (PSC volume) in addition to proxies for stratospheric aerosol loading, QBO, and solar cycle, all considered to be main drivers for ozone variability, are presented. It is shown that the main contribution to the recent increase in NH total ozone is from the combined effect of rising tropospheric driven planetary wave activity associated with reduced polar ozone loss at high latitudes as well as increasing solar activity. This conclusion can be drawn regardless of the use of linear trend or EESC terms in our statistical model. It is also clear that more years of data will be needed to further improve our estimates of the relative contributions of the individual processes to decadal ozone variability. The question remains if the observed increase in planetary wave driving is part of natural decadal atmospheric variability or will persist. If the latter is the case, it could be interpreted as a possible signature of climate change.

Long-term measurements of polar ozone show an unexpectedly large decadal scale variability in the mid-stratosphere during winter. Negative ozone anomalies are strongly correlated with the flux of energetic electrons in the radiation belt, which is modulated by the 11-year solar cycle. The magnitude of the observed decadal ozone changes (≈20%) is much larger than any previously reported solar cycle effect in the atmosphere up to this altitude. The early-winter ozone anomalies subsequently propagate downward into the lower stratosphere and may even influence total ozone and meteorological conditions during spring. These findings suggest a previously unrecognized mechanism by which solar variability impacts on climate through changes in polar ozone.

The Match technique was used to determine chemically induced ozone loss inside the stratospheric vortex during the Arctic winter 2002/2003. From end of November 2002, which is the earliest start of a Match campaign ever, until end of March 2003 approximately 800 ozonesondes were launched from 34 stations in the Arctic and mid latitudes. Ozone loss rates were quantified from the beginning of December until mid-March in the vertical region of 400–550 K potential temperature. In accordance with the occurrence of a large area of conditions favourable for the formation of polar stratospheric clouds in December ozone destruction rates varied between 10–15 ppbv/day depending on height. Maximum loss rates around 35 ppbv/day were reached during late January. Afterwards ozone loss rates decreased until mid-March when the final warming of the vortex began. In the period from 2 December 2002 to 16 March 2003 the accumulated ozone loss reduced the partial ozone column of 400–500 K potential temperature by 56±4 DU. This value is in good agreement with that inferred from the empirical relation of ozone loss against the volume of potential polar stratospheric clouds within the northern hemisphere. The sensitivity of the results on recent improvements of the approach has been tested.

The Match method quantifies chemical ozone loss in the polar stratosphere. The basic idea consists in calculating the forward trajectory of an air parcel that has been probed by an ozone measurement (e.g., by an ozonesonde or satellite instrument) and finding a second ozone measurement close to this trajectory. Such an event is called a 'match'. A rate of chemical ozone destruction can be obtained by a statistical analysis of several tens of such match events. Information on the uncertainty of the calculated rate can be inferred from the scatter of the ozone mixing ratio difference (second measurement minus first measurement) associated with individual matches. A standard analysis would assume that the errors of these differences are statistically independent. However, this assumption may be violated because different matches can share a common ozone measurement, so that the errors associated with these match events become statistically dependent. Taking this effect into account, we present an analysis of the uncertainty of the final Match result. It has been applied to Match data from the Arctic winters 1995, 1996, 2000, and 2003. For these ozonesonde Match studies the effect of the error correlation on the uncertainty estimates is rather small: compared to a standard error analysis, the uncertainty estimates increase by 15% on average. However, the effect may be more pronounced for typical satellite Match analyses: for an Antarctic satellite Match study (2003), the uncertainty estimates increase by 60% on average. The analysis showed that the random errors of the ozone measurements and the 'net match errors', which result from a displacement of the second ozone measurement of a match from the required position, are of similar magnitude. This demonstrates that the criteria for accepting a match (maximum trajectory duration, match radius, spread of trajectory clusters etc.) ensure that, given the unavoidable ozone-measurement errors, the magnitude of the net match errors is adequate. The estimate of the random errors of the ozonesonde measurements agrees well with laboratory results.

Future increases in the concentration of greenhouse gases and water vapour may cool the stratosphere further and increase the amount of polar stratospheric clouds (PSCs). Future Arctic PSC areas have been extrapolated from the highly significant trends 1958-2001. Using a tight correlation between PSC area and the total vortex ozone depletion and taking the decreasing amounts of ozone depleting substances into account we make empirical estimates of future ozone. The result is that Arctic ozone losses increase until 2010-2015 and decrease only slightly afterwards. However, for such a long extrapolation into the future caution is necessary. Tentatively taking the modelled decrease in the ozone trend in the future into account results in almost constant ozone depletions until 2020 and slight decreases afterwards. This approach is a complementary method of prediction to that based on the complex coupled chemistry-climate models (CCMs).