ALBERT

Description: The Antarctic ozone hole arises from ozone destruction driven by elevated levels of ozone destroying (active) chlorine in Antarctic spring. These elevated levels of active chlorine have to be formed first and then maintained throughout the period of ozone destruction. It is a matter of debate how this maintenance of active chlorine is brought about in Antarctic spring, when the rate of formation of HCl (considered to be the main chlorine deactivation mechanism in Antarctica) is extremely high. Here we show that in the heart of the ozone hole (16–18 km or 85–55 hPa, in the core of the vortex), high levels of active chlorine are maintained by effective chemical cycles (referred to as HCl null cycles hereafter). In these cycles, the formation of HCl is balanced by immediate reactivation, i.e. by immediate reformation of active chlorine. Under these conditions, polar stratospheric clouds sequester HNO3 and thereby cause NO2 concentrations to be low. These HCl null cycles allow active chlorine levels to be maintained in the Antarctic lower stratosphere and thus rapid ozone destruction to occur. For the observed almost complete activation of stratospheric chlorine in the lower stratosphere, the heterogeneous reaction HCl + HOCl is essential; the production of HOCl occurs via HO2 + ClO, with the HO2 resulting from CH2O photolysis. These results are important for assessing the impact of changes of the future stratospheric composition on the recovery of the ozone hole. Our simulations indicate that, in the lower stratosphere, future increased methane concentrations will not lead to enhanced chlorine deactivation (through the reaction CH4 + Cl  ⟶  HCl + CH3) and that extreme ozone destruction to levels below  ≈ 0.1 ppm will occur until mid-century.

Description: 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.

Description: 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.

Description: The 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 interactions between the ozone layer and climate. So far, climate models often use prescribed ozone fields, since a full stratospheric chemistry scheme is computationally very expensive. 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, 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 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 single processes and an independent validation of the different parameterizations for the single processes contained in the differential equations. The training of the original SWIFT model was based on fitting complete model runs to satellite observations and did not allow 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 SWIFT model are purely chemical rates of change in the new version, while the rates of change in the original SWIFT version 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 SWIFT model are validated with independent MLS satellite observations and the results of the original detailed chemistry model of ATLAS.

Description: 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, where 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 equations 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, local ozone column, mixing ratio of ozone and of the ozone depleting families (Cly, Bry, NOy and HOy). We will show that these 9 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. Nowadays, computers can 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.

Description: 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.

Description: 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.

Description: The Antarctic ozone hole arises from ozone destruction driven by elevated levels of ozone destroying (active) chlorine in Antarctic spring. These elevated levels of active chlorine have to be formed first and then maintained throughout the period of ozone destruction. It is a matter of debate, how this maintenance of active chlorine is brought about in Antarctic spring, when the rate of formation of HCl (considered to be the main chlorine deactivation mechanism in Antarctica) is extremely high. Here we show that in the heart of the ozone hole (16–18 km or 100–70 hPa, in the core of the vortex), high levels of active chlorine are maintained by effective chemical cycles (referred to as HCl null-cycles hereafter). In these cycles, the formation of HCl is balanced by immediate reactivation, i.e. by immediate reformation of active chlorine. Under these conditions, polar stratospheric clouds sequester HNO3 and thereby cause NO2 concentrations to be low. These HCl null-cycles allow active chlorine levels to be maintained in the Antarctic lower stratosphere and thus rapid ozone destruction to occur. For the observed almost complete activation of stratospheric chlorine in the lower stratosphere, the heterogeneous reaction HCl + HOCl, the production of HOCl via HO2 + ClO, with the HO2 resulting from CH2O photolysis, is essential. These results are important for assessing the impact of changes of the future stratospheric composition on the recovery of the ozone hole. Our simulations indicate that, in the lower stratosphere, future increased methane concentrations will not lead to enhanced chlorine deactivation (through the reaction CH4 + Cl → HCl + CH3) and that extreme ozone destruction to levels below ≈ 0.1 ppm will occur until mid-century.

Description: 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 reaction pathways and cycles involved in polar ozone depletion are well known, quantitative estimates of the importance of single 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 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, that is 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. Mixing ratios and reaction rates are obtained from runs of the ATLAS Chemistry and Transport Model driven by 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.

Description: We present a Lagrangian convective transport scheme developed for Chemistry and Transport Models and ensemble trajectory simulations. Similar to existing schemes in other Lagrangian models, it is based on a statistical approach of calculating parcel displacements by convection. These schemes redistribute air parcels within a fixed time step by calculating probabilities for entrainment and the altitude of detrainment. Our scheme extends this approach by modelling vertical updraft velocities and the time that an air parcel spends inside the convective event, which is important for simulating the tropospheric chemistry of short-lived species, e.g. it determines the time available for heterogeneous processes on the surface of cloud droplets. Two different schemes for determining the vertical updraft velocities are introduced, which are based on constant or random convective area fraction profiles, respectively. SO2 is used as an example to show that there is a significant effect on species mixing ratios when modelling the time spent in convective updrafts compared to a nearly instantaneous redistribution of air parcels. The 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 General Circulation Models. Validation runs driven by ECMWF ERA Interim reanalysis data are performed with the scheme implemented into the ATLAS Chemistry and Transport Model. These include long-term global trajectory simulations of Radon-222 that are compared to measurements, and runs testing mass conservation and the reproduction of the convective mass fluxes and detrainment rates of ERA Interim. Simulated vertical updraft velocities are validated by wind profiler measurements in Darwin.