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Hydrogen peroxide and higher organic hydroperoxides form an important reservoir for peroxy radicals (HOx), which are key contributors to the self-cleaning processes of the atmosphere. The work gives an overview of airborne in-situ trace gas observations of hydrogen peroxide (H2O2), and methyl hydroperoxide (MHP) over Europe during the Chemistry of the Atmosphere – Field Experiments in Europe (CAFE-EU, also BLUESKY) aircraft campaign. The purpose of the campaign was to obtain an overview of the trace gas and aerosol distribution over Europe to analyze atmospheric chemistry under the conditions of the COVID-19 lock-down. The campaign anticipated to investigate the impact of reduced emissions from anthropogenic sources due to the COVID-19 pandemic on the chemistry and physics of the atmosphere. The rapid decrease of anthropogenic emissions established a unique opportunity for analysis of the changes in the atmosphere. The campaign took place in May/June 2020 over Central and Southern Europe and within the North Atlantic Flight Corridor. Airborne measurements were performed on the High Altitude and Long-range (HALO) research aircraft out of the base of operation in Oberpfaffenhofen (Germany). Average mixing ratios for H2O2 of 0.32 ± 0.25 ppbv, 0.39 ± 0.23 ppbv and 0.38 ± 0.21 ppbv within the upper and middle troposphere and the boundary layer were measured over Europe, respectively. Vertical distribution of H2O2 reveals a significant decrease above the boundary layer in comparison with previous airborne observations, most likely due to cloud scavenging and subsequent rainout. The expected maximum hydrogen peroxide mixing ratios at 3 – 7 km were not found during BLUESKY in contrast to observations during previous studies over Europe, during the campaigns HOOVER and UTOPIHAN-ACT II/III. Simulations with the global chemistry-transport model EMAC reproduce partly the impact of cloud uptake and rainout loss of H2O2. A comparison of calculated deposition loss rates based on EMAC reveals an underestimation relative to the observations. A performed sensitivity study without H2O2 scavenging underlines the major impact of cloud processing and precipitation on the hydrogen peroxide budget. Differences between simulations and observations are most likely due to difficulties in the simulation of wet scavenging.

Atmospheric methane (CH4) has changed considerably in the time between the last glacial maximum (LGM) and the preindustrial period (PI). We investigate these changes in transient experiments with an Earth System Model, focusing on the rapid changes during the deglaciation, especially pronounced in the Bølling Allerød (BA) and Younger Dryas (YD) periods. We consider all relevant natural sources and sinks of methane and examine the drivers of changes in methane emissions as well as in the atmospheric lifetime of methane. We find that the evolution of atmospheric methane is largely driven by emissions from tropical wetlands, while variations in atmospheric lifetime are not negligible but small. Our model reproduces most changes in atmospheric methane very well, with the exception of the mid-Holocene decrease in methane, though the timing of ice sheet meltwater fluxes needs to be adjusted slightly in order to exactly reproduce the variations of the BA and YD.

We present high spatial resolution (up to 2.2×2.2 km2) simulations focussed over south-west Germany using the online coupled regional atmospheric chemistry model system MECO(n) (MESSy-fied ECHAM and COSMO models nested n times). Numerical simulation of nitrogen dioxide (NO2) surface volume mixing ratios (VMRs) are compared to in situ measurements from a network with 193 locations including background, traffic-adjacent and industrial stations to investigate the model's performance in simulating the spatial and temporal variability of short-lived chemical species. We show that the use of a high-resolution and up-to-date emission inventory is crucial for reproducing the spatial variability and resulted in good agreement with the measured VMRs at the background and industrial locations with an overall bias of less than 10 %. We introduce a computationally efficient approach that simulates diurnal and daily variability in monthly-resolved anthropogenic emissions to resolve the temporal variability of NO2. MAX-DOAS (Multiple AXis Differential Optical Absorption Spectroscopy) measurements performed at Mainz (49.99∘ N, 8.23∘ E) were used to evaluate the simulated tropospheric vertical column densities (VCDs) of NO2. We propose a consistent and robust approach to evaluate the vertical distribution of NO2 in the boundary layer by comparing the individual differential slant column densities (dSCDs) at various elevation angles. This approach considers details of the spatial heterogeneity and sensitivity volume of the MAX-DOAS measurements while comparing the measured and simulated dSCDs. The effects of clouds on the agreement between MAX-DOAS measurements and simulations have also been investigated. For low elevation angles (≤8∘), small biases in the range of −14 % to +7 % and Pearson correlation coefficients in the range of 0.5 to 0.8 were achieved for different azimuth directions in the cloud-free cases, indicating good model performance in the layers close to the surface. Accounting for diurnal and daily variability in the monthly-resolved anthropogenic emissions was found to be crucial for the accurate representation of time series of measured NO2 VMR and dSCDs and is particularly critical when vertical mixing is suppressed, and the atmospheric lifetime of NO2 is relatively long.

Between the last glacial maximum (LGM) and preindustrial times (PI), the atmospheric concentration of CH4, as shown by reconstructions from ice cores, roughly doubled. It then doubled again from PI to the present. Ice cores, however, cannot tell us how that development will continue in the future, and ice cores also cannot shed light on the causes of the rise in methane, as well as the rapid fluctuations during periods such as the Bolling-Allerod and Younger Dryas.We use a methane-enabled version of MPI-ESM, the Max Planck Institute for Meteorology Earth System Model, to investigate changes in methane cycling in a transient ESM experiment from the LGM to the present, continuing onwards into the future for the next millennium. The model is driven by prescribed orbit, greenhouse gases and ice sheets, with all other changes to the climate system determined internally. Methane cycling is modelled by modules representing the atmospheric transport and sink of methane, as well as terrestrial sources and sinks from soils, termites, and fires. Thus, the full natural methane cycle – with the exception of geological and animal emissions – is represented in the model. For historical and future climate, anthropogenic emissions of methane are considered, too.We show that the methane increase since the LGM is largely driven by source changes, with LGM emissions substantially reduced in comparison to the early Holocene and preindustrial states due to lower temperature, CO2, and soil carbon. Depending on the future climate scenario, these dependencies then lead to further increases in CH4, with a further doubling of atmospheric CH4 easily possible if one of the higher radiative forcing scenarios is followed. Furthermore, the future increases in CH4 will persist for a long time, as CH4 only decreases when the climate system cools again.

Regional atmospheric chemistry models are adopted for simulating concentrations of atmospheric components at high resolution and quantifying the impact of localized emissions (e.g. industrial and urban clusters) on the non-linear chemical processes, e.g. ozone production. However, their evaluation is challenging due to the limited availability of high spatiotemporally resolved reference datasets. For the same reason, the vertical distribution of pollutants simulated by the model is especially arduous to assess.Here, we present regional atmospheric chemistry model studies with spatial resolution up to 2.2 × 2.2 km2 focused around Germany for May 2018 using the MECO(n) model system. Using a network of surface concentration measurements at background, near traffic and industrial locations, we evaluate the spatial distribution of NO2 simulated by the model. The highly resolved model together with a comparable resolution and up-to-date input emissions inventory, was found to perform best in reproducing the spatial distribution of NO2 surface volume mixing ratios (VMRs). We propose a computationally efficient approach to account for the diurnal and day of the week variability of input anthropogenic emissions (e.g. from road transport), which proved to be crucial for resolving the temporal variability of NO2 surface VMRs.The simulated NO2 tropospheric vertical column densities were evaluated by employing the measurements of a 4-azimuth MAX-DOAS instrument in Mainz. Generally, such comparisons do not account for the spatial sensitivity volume of the MAX-DOAS measurements, the change of sensitivity within this volume and the spatial heterogeneity of NO2. We therefore apply a consistent approach of comparison of the differential slant column densities (dSCDs), which overcomes these limitations. Moreover, the dSCDs are obtained for several elevation and azimuth angles, which are characterized by distinctive sensitivity for different vertical levels within the boundary layer and different horizontal representativeness. Hence, also an evaluation of the model in simulating the vertical distribution of NO2 can be performed with this approach using continuous MAX-DOAS measurements spanning long time periods. We found that the model performs well with respect to the measured dSCDs at low elevation angles (< 8°) with an overall bias between +14 and -9%, and Pearson correlation coefficients between 0.5 and 0.8 for the different azimuth viewing directions.

We present high spatial resolution (up to 2.2 × 2.2 km2 simulations focussed over south-west Germany using the online coupled regional atmospheric chemistry model system MECO(n). Numerical simulation of nitrogen dioxide (NO2) surface volume mixing ratios (VMR) are compared to in situ measurements from a network with 193 locations including background, traffic-adjacent and industrial stations to investigate the model's performance in simulating the spatial and temporal variability of short-lived chemical species. We show that the use of a high-resolution and up-to-date emission inventory is crucial for reproducing the spatial variability, and resulted in good agreement with the measured VMRs at the background and industrial locations with an overall bias of less than 10 %. We introduce a computationally efficient approach that simulates diurnal and daily variability in monthly resolved anthropogenic emissions to resolve the temporal variability of NO2. MAX-DOAS measurements performed at Mainz (49.99° N, 8.23° E) were used to evaluate the simulated tropospheric vertical column densities (VCD) of NO2. We propose a consistent and robust approach to evaluate the vertical distribution of NO2 in the boundary layer by comparing the individual differential slant column densities (dSCDs) at various elevation angles. This approach considers details of the spatial heterogeneity and sensitivity volume of the MAX-DOAS measurements while comparing the measured and simulated dSCDs. The effects of clouds on the agreement between MAX-DOAS measurements and simulations have also been investigated. For low elevation angles ≤ 8°), small biases in the range of −14 to +7 % and Pearson correlation coefficients in the range of 0.5 to 0.8 were achieved for different azimuth directions in the cloud-free cases indicating good model performance in the layers close to the surface. Accounting for diurnal and daily variability in the monthly resolved anthropogenic emissions was found to be crucial for the accurate representation of time series of measured NO2 VMR and dSCDs and is particularly critical when the atmospheric lifetime of NO2 is relatively long.

The time between the last glacial maximum (LGM) and the present is highly interesting with regard to atmospheric methane. Between the LGM and 10 ka BP atmospheric CH4, as reconstructed from ice cores, nearly doubled, with very rapid concentration changes of about 200 ppb occurring during the Bølling Allerød (BA) and Younger Dryas (YD) transitions. During the Holocene, atmospheric CH4 is very similar for 10 ka BP and PI, but CH4 is about 15% lower in between at 5 ka BP.We use a methane-enabled version of MPI-ESM, the Max Planck Institute Earth System Model, to investigate changes in methane cycling in a transient ESM experiment from the LGM to the present. The model is driven by prescribed orbit, greenhouse gases and ice sheets, with all other changes to the climate system determined internally. Methane cycling is modelled by modules representing the atmospheric transport and sink of methane, as well as terrestrial sources and sinks from soils, termites, and fires. Thus, the full natural methane cycle – with the exception of geological and animal emissions – is represented in the model.Model results are compared to methane concentrations from ice cores, and key periods in climate/methane evolution are highlighted by detailed analyses. Methane concentrations can mainly be explained by emission changes, with LGM emissions substantially reduced in comparison to the early Holocene and preindustrial states due to lower temperature, CO2, and soil carbon. For the large transitions during the deglaciation, such as the transitions from Older Dryas to BA, BA to YD, and YD to Holocene, ocean circulation changes are required to obtain atmospheric methane changes of sufficient magnitude and rapidity.

Regional chemistry-transport models typically simulate the physical and chemical state of the atmosphere at a high spatial resolution, e.g. of less than 7 km. At this relatively high spatial resolution, air quality and relevant processes within cities can be assessed to facilitate strategic mitigation planning. Comparison of regional models with satellite and ground-based observations helps validate the models and evaluate emission inventories, as well as satellite retrieval algorithms. For example, an underestimation of atmospheric trace gases (like often found for NO2) by satellite observations can be improved by providing high-resolution input fields from regional models.MECO(n), a global-to-regional chemistry climate modeling system, in which the finer resolved domains receive their initial and boundary conditions on-line from the next coarser model instance, was set-up with Germany as focus. 1-way nested MECO(3) simulations were performed for May 2018 with spatial resolution up to ~2.2 km × 2.2 km in the finest domain. Model simulations accounting separately for both TNO MACC III and EDGAR 4.3.2 anthropogenic emissions are evaluated against TROPOMI observations. A diurnal factor was applied to road transport emissions to account for their temporal variation. For the comparison with TROPOMI data, we applied a novel method of online sampling of model fields along the satellite overpass by also accounting for the difference in local solar time across the swath width, which can be up to 90 minutes. Modified airmass factors in the TROPOMI data product, using the model calculated NO2 a priori profiles and taking into account averaging kernels, resulted in an improved agreement of the spatial pattern of NO2 vertical column density (VCD) between model and satellite.NO2 VCDs over Mainz, calculated using model output at the finest model resolution, were compared against MAX-DOAS observations for the simulation period. Vertical profiles of NO2 were also retrieved in 4 azimuth directions around Mainz by profile inversion of MAX-DOAS measurements. The temporal (e.g. day-to-day and diurnal) variation of the 3-D NO2 field derived from the model was evaluated against the MAX-DOAS observations. For the cloud-free days, the model is able to reproduce the temporal development with satisfactory temporal correlation (slope=0.7, r=0.5) of the NO2 VCDs. For a direct comparison of measured slant column densities of NO2, height-resolved 2-D box airmass factors were calculated using McArtim (Monte Carlo Atmospheric radiative transfer model) and applied to the modelled trace gas profiles along individual elevation angles of the measurements. This comparison procedure accounts for the complex dependency of the MAX-DOAS column densities on the 3D (vertical and horizontal) trace gas distribution in the measurement direction.

This study uses the EMAC atmospheric chemistry-climate model to simulate cloud properties with a prognostic cloud droplet nucleation scheme. We present modeled global distributions of cloud condensation nuclei (CCN) number concentrations and CCN activation rates, together with the effective hygroscopicity parameter κ, to describe the aerosol chemical composition effect on CCN activation. Large particles can easily activate into cloud droplets, even at low κ values due to the dominant size effect in cloud droplet formation. Small particles are less efficiently activated as CCN, and are more sensitive to aerosol composition and supersaturation. Since the dominant fraction of small particles generally originates from anthropogenic precursor emissions over land, this study focuses on the influence of the continental atmosphere, using a prognostic cloud droplet nucleation scheme that considers aerosol-cloud interactions during cloud formation, together with a double-moment cloud microphysics scheme. The agreement of simulated clouds and climate with observations generally improves over the Northern Hemisphere continents, particularly high air pollution regions such as Eastern US, Europe, East Asia by accounting for aerosol-cloud interactions that include impacts of chemical composition on CCN activation.

Aerosol-cloud-climate interactions (ACI) involve the activation of aerosol particles, acting as cloud condensation nuclei (CCN), into cloud droplets and their influence on planetary albedo and climate, which have been incorporated in a general circulation model. CCN activation is calculated using aerosol physical and chemical characteristics in cloud droplet nucleation (CDN) schemes. We applied three different CDN schemes to study the variability of climate predictions from aerosol-cloud interactions using the ECHAM5/MESSy Atmospheric Chemistry-climate model (EMAC). Tuning has been performed for each simulation to achieve net radiative balance at the top of the atmosphere. EMAC generally performs well in simulating climate in comparison to observations. The choice of CDN scheme has a large impact on estimated cloud radiative effects especially in regions with high anthropogenic fine particle pollution. Most pronounced regional variability is found in Europe, India, and China. This is mainly due to differences in the calculated CCN activation of small (Aitken) size particles. Kohler methods, which consider both aerosol physical and chemical properties in the CDN calculations, are recommended for investigating anthropogenic aerosol effects on climate. The tuning process towards radiative balance confines these impacts and can be regarded as important as the choice of CDN scheme. Regional variability is also found in Central Africa and South America, related to the high sensitivity of cloud optical parameter tuning as well as differences among CDNC. The tunable parameters affect the water budget and cloud optical properties, and the sensitivity of CDN. The overall variability of simulated climate, induced by different CDN schemes, is found to be less than 27%, which can be restricted by parameter tuning. In general, tuning tends to improve the general performance of the climate model, but not necessarily for all variables. We find that it is important to consider the regional sensitivity of various CCN activation and tuning parameters to optimally simulate climate.

Enhanced aerosol abundance in the upper troposphere and lower stratosphere (UTLS) associated with the Asian summer monsoon (ASM) is referred to as the Asian Tropopause Aerosol Layer (ATAL). The chemical composition, microphysical properties, and climate effects of aerosols in the ATAL have been the subject of discussion over the past decade. In this work, we use the ECHAM/MESSy Atmospheric Chemistry (EMAC) general circulation model at a relatively fine grid resolution (about 1.1×1.1∘) to numerically simulate the emissions, chemistry, and transport of aerosols and their precursors in the UTLS within the ASM anticyclone during the years 2010–2012. We find a pronounced maximum of aerosol extinction in the UTLS over the Tibetan Plateau, which to a large extent is caused by mineral dust emitted from the northern Tibetan Plateau and slope areas, lofted to an altitude of at least 10 km, and accumulating within the anticyclonic circulation. We also find that the emissions and convection of ammonia in the central main body of the Tibetan Plateau make a great contribution to the enhancement of gas-phase NH3 in the UTLS over the Tibetan Plateau and ASM anticyclone region. Our simulations show that mineral dust, water-soluble compounds, such as nitrate and sulfate, and associated liquid water dominate aerosol extinction in the UTLS within the ASM anticyclone. Due to shielding of high background sulfate concentrations outside the anticyclone from volcanoes, a relative minimum of aerosol extinction within the anticyclone in the lower stratosphere is simulated, being most pronounced in 2011, when the Nabro eruption occurred. In contrast to mineral dust and nitrate concentrations, sulfate increases with increasing altitude due to the larger volcano effects in the lower stratosphere compared to the upper troposphere. Our study indicates that the UTLS over the Tibetan Plateau can act as a well-defined conduit for natural and anthropogenic gases and aerosols into the stratosphere.

The Modular Earth Submodel System (MESSy) provides an interface to couple submodels to a basemodel via a highly flexible data management facility (Jöckel et al., 2010). In the present paper we present the four new radiation related submodels RAD, AEROPT, CLOUDOPT and ORBIT. The submodel RAD (with shortwave radiation scheme RAD_FUBRAD) simulates the radiative transfer, the submodel AEROPT calculates the aerosol optical properties, the submodel CLOUDOPT calculates the cloud optical properties, and the submodel ORBIT is responsible for Earth orbit calculations. These submodels are coupled via the standard MESSy infrastructure and are largely based on the original radiation scheme of the general circulation model ECHAM5, however, expanded with additional features. These features comprise, among others, user-friendly and flexibly controllable (by namelists) on-line radiative forcing calculations by multiple diagnostic calls of the radiation routines. With this, it is now possible to calculate radiative forcing (instantaneous as well as stratosphere adjusted) of various greenhouse gases simultaneously in only one simulation, as well as the radiative forcing of cloud perturbations. Examples of on-line radiative forcing calculations in the ECHAM/MESSy Atmospheric Chemistry (EMAC) model are presented.

K. J. Pringle1,2, H. Tost1, S. Metzger1, B. Steil1, D. Giannadaki1, A. Nenes3, C. Fountoukis4, P. Stier5, E. Vignati6, and J. Lelieveld1,7 1Max Planck Institute for Chemistry, Mainz, Germany 2School of Earth and Environment, University of Leeds, Leeds, UK 3Schools of Earth & Atmospheric Sciences and Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA 4Institute of Chemical Engineering and High Temperature Chemical Processes, Foundation for Research and Technology – Hellas, Patras, Greece 5Atmospheric, Oceanic and Planetary Physics, Department of Physics, University of Oxford, Oxford, UK 6Joint Research Centre, Institute for Environment and Sustainability, Climate Change Unit, Ispra, Italy 7The Cyprus Institute, Energy, Environment and Water Research Centre, Nicosia, Cyprus

We scrutinize the importance of aerosol water for the aerosol optical depth (AOD) calculations by a long-term evaluation of the EQuilibrium Simplified Aerosol Model V4 for climate modeling, which was introduced by Metzger et al. (2016a). EQSAM4clim is based on a sin-gle solute coefficient approach that efficiently parameterizes hygroscopic growth, account- ing for aerosol water uptake from the deliquescence relative humidity up to supersaturation. EQSAM4clim extends the single solute coefficient approach to treat water uptake of multi- component mixtures. The gas-aerosol partitioning and the mixed solution water uptake can be solved analytically, preventing the need for iterations, which is computationally efficient. EQSAM4clim has been implemented in the global chemistry climate model EMAC and com- pared to ISORROPIA II (Fountoukis and Nenes, 2007) at climate time-scales. Our global modeling results show that (I) our EMAC results of the aerosol optical depth (AOD) are comparable to independent results of Pozzer et al. (2015) for the period 2000–2010, (II) the results of various aerosol properties of EQSAM4clim and ISORROPIA II are similar and in agreement with AERONET and EMEP observations for the period 2000–2013, and (III) that the underlying assumptions on the aerosol water uptake limitations are important for derived AOD calculations. Sensitivity studies of different levels of chemical aging and associated water uptake show larger effects on AOD calculations for the year 2005 compared to the differences associated with the application of the two gas-liquid-solid partitioning schemes. Altogether, our study reveals the importance of the aerosol water for climate applications.

The modelling of aerosol radiative forcing is a major cause of uncertainty in the assessment of global and regional atmospheric energy budgets and climate change. One reason is the strong dependence of the aerosol optical properties on the mixing state of aerosol components, such as absorbing black carbon and, predominantly scattering sulfates. Using a new column version of the aerosol optical properties and radiative-transfer code of the ECHAM/MESSy atmospheric-chemistry–climate model (EMAC), we study the radiative transfer applying various mixing states. The aerosol optics code builds on the AEROPT (AERosol OPTical properties) submodel, which assumes homogeneous internal mixing utilising the volume average refractive index mixing rule. We have extended the submodel to additionally account for external mixing, partial external mixing and multilayered particles. Furthermore, we have implemented the volume average dielectric constant and Maxwell Garnett mixing rule. We performed regional case studies considering columns over China, India and Africa, corroborating much stronger absorption by internal than external mixtures. Well-mixed aerosol is a good approximation for particles with a black-carbon core, whereas particles with black carbon at the surface absorb significantly less. Based on a model simulation for the year 2005, we calculate that the global aerosol direct radiative forcing for homogeneous internal mixing differs from that for external mixing by about 0.5 W m−2.

[1] The Active Red Sea Trough (ARST) is an infrequent weather phenomenon that is associated with extreme precipitation, flash floods, and severe societal impacts in the Middle East (ME). Using reanalysis (ERA-Interim) and observational precipitation (Aphrodite and stations) data, we investigate its underlying dynamics, geographical extent, and seasonality. Twelve ARST events affecting the Levant have the same dynamical characteristics as those associated with a major flood in Jeddah (Saudi Arabia) on 25 November 2009. Hence, the Jeddah flooding was caused by an ARST, which implies that ARSTs can affect a much larger part of the ME than previously assumed. We present an ARST concept involving six dynamical factors: (1) a low-level trough; the Red Sea Trough (RST), (2) an anticyclone over the Arabian Peninsula; the Arabian Anticyclone (AA), (3) a transient midlatitude upper trough, (4) an intensified subtropical jet stream, (5) moisture transport pathways, and (6) strong ascent resulting from tropospheric instability and the synoptic-scale dynamical forcing. We explain the ARST as the interaction of a persistent stationary wave in the tropical easterlies (i.e., the RST) with a superimposed amplifying Rossby wave, resulting in northward propagating moist air masses over the Red Sea. Our findings emphasize the relevance of the AA, causing moisture transport from the Arabian and Red Seas. The particular topography in the Red Sea region and associated low-level circulation makes the ARST unique among tropical-extratropical interactions. The ARST seasonality is explained by the large-scale circulation and in particular the seasonal cycle of the semipermanent quasi-stationary RST and AA.

Transatlantic dust transport has many implications for the atmosphere, ocean and climate. We present a modeling study on the impact of the key processes (dust emissions flux, convection and dust aging parameterizations) that control the transatlantic dust transport. Typically, the Inter-Tropical Convergence Zone (ITCZ) acts as a barrier for the meridional dust transport. To characterize the dust outflow over the Atlantic Ocean, we address two regional phenomena: (i) dust interactions with the ITCZ (DIZ) and (ii) the adjacent dust transport over the Atlantic Ocean (DTA). In the DTA zone, the dust loading shows a steep and linear gradient westward over the Atlantic Ocean where particle sedimentation is the dominant removal process, whereas in the DIZ zone cloud interactions and wet deposition predominate. To study the different impacts of aging, we present two case studies that exclude condensation and coagulation, and include dust aging at various levels of complexity. For dust aging, we consider the uptake of inorganic acids on the surface of mineral particles that form salt compounds. Calcium, used as a proxy for the overall chemically reactive dust fraction, drives the dust-related neutralization reactions leading to higher dust aerosol optical depth (AOD). The aged dust particles are transferred to the soluble aerosol modes in the model and are mixed with other species that originate from anthropogenic and natural sources. The neutralization products (salts) take up water vapor from the atmosphere and increase the dust AOD under subsaturated conditions. We define the "direct effect of dust aging" to refer to the increase in AOD as a result of hygroscopic growth. On the other hand, the aged dust is more efficiently removed (wet and dry) because of the increase in particle size and hygroscopicity. This more efficient removal reduces the dust AOD over the DIZ zone. We define this as the "indirect effect of dust aging", complementary to the direct effect that is dominant in the DTA zone. Distinction of the two aging effects helps develop insight into the regional importance of dust–air-pollution interactions.

We simulate twenty, perpetual Januaries each under solar minimum and maximum conditions using the Freie Universitat Berlin Climate Middle Atmosphere Model with interactive chemistry (FUB CMAM CHEM), including the 27-day solar rotational cycle. Cross-correlation functions (r) of tropical ozone and ultraviolet (UV) suggest peak values of +0.5 to +0.6 (with % changes in ozone of 0.4–0.6%) in the middle atmosphere. Temperature in the middle atmosphere varies with UV by up to 0.5 K, which appears to be mainly dynamical in origin. We calculate a signal associated with the rotational cycle in the troposphere, although this requires further investigations.

The chemistry climate model ECHAM5/MESSy1 (E5/M1) in a setup extending from the surface to 80 km with a vertical resolution of about 600 m near the tropopause with nudged tropospheric meteorology allows a direct comparison with satellite data of chemical species at the same time and location. Here we present results out of a transient 10~years simulation for the period of the Antarctic vortex split in September 2002, where data of MIPAS on the ENVISAT-satellite are available. For the first time this satellite instrument opens the opportunity, to evaluate all stratospheric nitrogen containing species simultaneously with a good global coverage, including the source gas N2O and ozone which allows an estimate for NOx-production in the stratosphere. We show correlations between simulated and observed species in the altitude region between 10 and 50 hpa for different latitude belts, together with the Probability Density Functions (PDFs) of model results and observations. This is supplemented by global maps on pressure levels showing the comparison between the satellite and the simulated data sampled at the same time and location. We demonstrate that the model in most cases captures the partitioning in the nitrogen family, the diurnal cycles and the spatial distribution within experimental uncertainty. This includes even variations due to tropospheric clouds. There appears to be, however, a problem to reproduce the observed nighttime partitioning between N2O5 and NO2 in the middle stratosphere using the recommended set of reaction coefficients and photolysis data.

Several stratospheric chemistry modules from box, 2-D or 3-D models, have been intercompared. The intercomparison was focused on the ozone loss and associated reactive species under the conditions found in the cold, wintertime Arctic and Antarctic vortices. Comparisons of both gas phase and heterogeneous chemistry modules show excellent agreement between the models under constrained conditions for photolysis and the microphysics of polar stratospheric clouds. While the mean integral ozone loss ranges from 4–80% for different 30–50 days long air parcel trajectories, the mean scatter of model results around these values is only about ±1.5%. In a case study, where the models employed their standard photolysis and microphysical schemes, the variation around the mean percentage ozone loss increases to about ±7%. This increased scatter of model results is mainly due to the different treatment of the PSC microphysics and heterogeneous chemistry in the models, whereby the most unrealistic assumptions about PSC processes consequently lead to the least representative ozone chemistry. Furthermore, for this case study the model results for the ozone mixing ratios at different altitudes were compared with a measured ozone profile to investigate the extent to which models reproduce the stratospheric ozone losses. It was found that mainly in the height range of strong ozone depletion all models underestimate the ozone loss by about a factor of two. This finding corroborates earlier studies and implies a general deficiency in our understanding of the stratospheric ozone loss chemistry rather than a specific problem related to a particular model simulation.

The Mediterranean Intensive Oxidant Study, performed in the summer of 2001, uncovered air pollution layers from the surface to an altitude of 15 kilometers. In the boundary layer, air pollution standards are exceeded throughout the region, caused by West and East European pollution from the north. Aerosol particles also reduce solar radiation penetration to the surface, which can suppress precipitation. In the middle troposphere, Asian and to a lesser extent North American pollution is transported from the west. Additional Asian pollution from the east, transported from the monsoon in the upper troposphere, crosses the Mediterranean tropopause, which pollutes the lower stratosphere at middle latitudes.

The modelling of aerosol radiative forcing is a major cause of uncertainty in the assessment of global and regional atmospheric energy budgets and climate change. One reason is the strong dependence of the aerosol optical properties on the mixing state of aerosol components like black carbon and sulphates. Using a new column version of the aerosol optical properties and radiative transfer code of the atmospheric chemistry-climate model EMAC, we study the radiative transfer applying various mixing states. The aerosol optics code builds on the AEROPT submodel which assumes homogeneous internal mixing utilising the volume average refractive index mixing rule. We have extended the submodel to additionally account for external mixing, partial external mixing and multi-layered particles. Furthermore, we have implemented the volume average dielectric-constant and Maxwell Garnett Mixing rule. We performed regional case studies considering columns over China, India and Africa, corroborating much stronger absorption by internal than external mixtures. Well mixed aerosol is a good approximation for particles with a black carbon core, whereas particles with black carbon at the surface absorb significantly less. Based on a model simulation for the year 2005 we calculate that the global aerosol direct radiative-forcing for homogeneous internal mixing differs from that for external mixing by about 0.5 W m−2.

The development of the future atmospheric chemical composition is investigated with respect to NO y and O 3 by means of the off-line coupled dynamic-chemical general circulation model ECHAM3/CHEM. Two time slice experiments have been performed for the years 1992 and 2015, which include changes in sea surface temperatures, greenhouse gas concentrations, emissions of CFCs, NO x and other species, i.e., the 2015 simulation accounts for changes in chemically relevant emissions and for a climate change and its impact on air chemistry. The 2015 simulation clearly shows a global increase in ozone except for large areas of the lower stratosphere, where no significant changes or even decreases in the ozone concentration are found. For a better understanding of the importance of (A) emissions like NO x and CFCs, (B) future changes of air temperature and water vapour concentration, and (C) other dynamical parameters, like precipitation and changes in the circulation, diabatic circulation, stratosphere-troposphere-exchange, the simulation of the future atmosphere has been performed stepwise. This method requires a climate-chemistry model without interactive coupling of chemical species. Model results show that the direct effect of emissions (A) plays a major role for the composition of the future atmosphere, but they also clearly show that climate change (B and C) has a significant impact and strongly reduces the NO y and ozone concentration in the lower stratosphere. DOI: 10.1034/j.1600-0889.2001.d01-10.x

A fundamental difficulty in 3-D models is addressed which can arise due to inconsistencies between advection schemes and winds. It is shown that a model will fail to meet certain basic criteria, desired of 3-D transport models, when the density field computed by the advection scheme from the winds differs from the implied density field based on the surface pressure and the sigma (or hybrid) coordinates. To allow a rigorous mathematical formulation, the focus is on the example of a mass flux advection scheme in a model where the winds and surface pressure are derived from different advection schemes (e.g. a spectral scheme in a climate model or a weather centre model); however, in principle the discussion applies to nearly any situation in which the pressure levels change in a model. To illustrate the potential severity of such problems, a mass conserving grid-to-grid transformation scheme is constructed which only uses the current tracer mass mixing-ratio distribution. It is shown that only one solution exists that is comprehensively valid for any arbitrary tracer distribution, and that this type of correction introduces an additional undesired artificial vertical diffusion component into the model transport that increases with increasing tracer mass mixing-ratio gradients and may exceed the physical vertical transport itself. It is demonstrated that the results of any supplementary fix, either mass fixer or grid-to-grid transformation, are generally unacceptable for global modelling applications. From this, it is concluded that the only alternative which can produce reliable results for any arbitrary tracer is to maintain a consistent grid throughout the entire model time step, where all changes in pressure levels due to modelled advection exactly match the changes implied by the surface pressure at the next time step. Although this is already done in some models, this would require significant changes in the structure of the advection scheme or its input wind fields in several other contemporary general circulation and chemistry transport models.

The future development of stratospheric ozone layer depends on the concentration of chlorine and bromine containing species. The stratosphere is also expected to be affected by future enhanced concentrations of greenhouse gases. These result in a cooling of the winter polar stratosphere and to more stable polar vortices which leads to enhanced chemical depletion and reduced transport of ozone into high latitudes. One of the driving forces behind the interest in stratospheric ozone is the impact of ozone on solar UV-B radiation. In this study UV scenarios have been constructed based on ozone predictions from the chemistry-climate model runs carried out by GISS, UKMO and DLR. Since cloudiness, albedo and terrain height are also important factors, climatological values of these quantities are taken into account in the UV calculations. Relative to 1979–92 conditions, for the 2010–2020 time period the GISS model results indicate a springtime enhancement of erythemal UV doses of up to 90% in the 60–90 °N region and an enhancement of 100% in the 60–90 °S region. The corresponding maximum increases in the annual Northern Hemispheric UV doses are estimated to be 14% in 2010–20, and 2% in 2040–50. In the Southern Hemisphere 40% enhancement is expected during 2010–20 and 27% during 2040–50.

The role of acetone and PAN in the chemistry of the upper troposphere has been investigated with a time-dependent photochemical box model. The results show that acetone strongly enhances aircraft-related ozone production, as exemplified in this study over North Atlantic during summer. For typical flight corridor conditions, the inclusion of about 1 nmol mol −1 acetone more than doubles net ozone production by aircraft NO emissions and resolves discrepancies between observations and several global model predictions. The actual magnitude of the acetone-attributed enhancement of ozone production can, however, be reduced by PAN formation which acts as a sink for NOx (NO+NO2) and also lowers the OH/HO2 ratio.

The importance of dynamics for stratospheric ozone distribution in the northern hemisphere is investigated by using multiannual simulations of the coupled dynamic-chemical general circulation model ECHAM3/CHEM. This model includes a parameterization for heterogeneous reactions on the surfaces of polar stratospheric clouds (PSCs) and on sulfate aerosols. A warm and a cold stratospheric winter are examined to estimate the range of chemical ozone loss in the model due to heterogeneous reactions on PSCs. Ozone depletion in the model mainly occurs inside the polar vortex. An additional ozone reduction due to heterogeneous reactions on PSCs is found outside the polar vortex. Secondary vortex formation and vortex contraction after an elongation lead to a transport of air masses with chemically reduced ozone values out of the vortex. Except for such events the edge of the modeled polar vortex acts as a barrier to transport. During the formation of secondary vortices no additional heterogeneous reactions occur therein. Other dynamic events, such as the elongation of the polar vortex and its displacement to lower latitudes, lead to an intense ozone depletion. A minor stratospheric warming in the model causes a total deactivation of chlorine compounds and prevents further ozone depletion. In midlatitudes, the amplitude of short-term variations of total ozone is amplified by PSC heterogeneous chemical ozone reduction.

ECHAM3/CHEM is used to estimate the future development of the ozone layer. The general circulation model ECHAM3 and the chemistry module CHEM are coupled in a CTM-like mode, i.e. no feedback of simulated chemical species on radiation is considered. Currently CHEM does not include bromine chemistry. Two time-slice experiments representing 1991 and 2015 conditions are carried out. Chemical species are transported by winds calculated with different CO 2 mixing ratios as a proxy for other greenhouse-gases. For 2015, the adopted increase of CO 2 and the corresponding modification of the sea-surface temperature lead to a warming of the troposphere and a cooling of the stratosphere. The assessment for 2015 indicates that the ozone layer will not homogeneously recover, despite the employed decrease of chlorine in the model. Whereas in low and mid-latitudes an ascent of stratospheric O 3 is obvious, no significant increase of O 3 is found in the polar regions during spring time.

The global three-dimensional dynamic-chemical model ECHAM3/CHEM is employed to estimate the impact of present and future sub- and supersonic aircraft NOx emissions on ozone. Multinual simulations are performed to investigate changes of large-scale climatological features. An increase of tropospheric ozone of 3–4% is found in the Northern Hemisphere for a present day scenario, independently from season. No indications for significant ozone changes are indicated in the lower stratosphere. NOx emissions expected for the year 2015 by sub- and supersonic (500 civil aircraft, Mach 2.4, EINOx=15) air traffic yield much larger ozone changes in the model. An ozone increase of approximately 15% is predicted near the cruise altitude of future subsonic air traffic. This is accompanied by a clear ozone reduction of 3–4% in the lower stratosphere caused by supersonic aircraft. A stronger decrease of ozone is detected in polar winter due to the impact of heterogeneous reactions on polar stratospheric clouds.

Water is a main component of atmospheric aerosols and its amount depends on the particle chemical composition. We introduce a new parameterization for the aerosol hygroscopic growth factor (HGF), based on an empirical relation between water activity (aw) and solute molality (μs) through a single solute specific coefficient νi. Three main advantages are: (1) wide applicability, (2) simplicity and (3) analytical nature. (1) Our approach considers the Kelvin effect and covers ideal solutions at large relative humidity (RH), including CCN activation, as well as concentrated solutions with high ionic strength at low RH such as the relative humidity of deliquescence (RHD). (2) A single νi coefficient suffices to parameterize the HGF for a wide range of particle sizes, from nanometer nucleation mode to micrometer coarse mode particles. (3) In contrast to previous methods, our analytical aw parameterization depends not only on a linear correction factor for the solute molality, instead νi also appears in the exponent in form x · ax. According to our findings, νi can be assumed constant for the entire aw range (0–1). Thus, the νi based method is computationally efficient. In this work we focus on single solute solutions, where νi is pre-determined with the bisection method from our analytical equations using RHD measurements and the saturation molality μssat. The computed aerosol HGF and supersaturation (Köhler-theory) compare well with the results of the thermodynamic reference model E-AIM for the key compounds NaCl and (NH4)2SO4 relevant for CCN modeling and calibration studies. The equations introduced here provide the basis of our revised gas-liquid-solid partitioning model, i.e. version 4 of the EQuilibrium Simplified Aerosol Model (EQSAM4), described in a companion paper.

The submodel PSC of the ECHAM5/MESSy Atmospheric Chemistry model (EMAC) has been developed to simulate the main types of polar stratospheric clouds (PSC). The parameterisation of the supercooled ternary solutions (STS, type 1b PSC) in the submodel is based on Carslaw et al. (1995b), the thermodynamical approach to simulate ice particles (type 2 PSC) on Marti and Mauersberger (1993). For the formation of nitric acid trihydrate (NAT) particles (type 1a PSC) two different parameterisations exist. The first one is based on an instantaneous thermodynamical approach from Hanson and Mauersberger (1988), the second one (new implemented by Kirner, 2008) considers the growth of the NAT particles with aid of a surface growth factor based on Carslaw et al. (2002). Via namelist switches the NAT parameterisation, as well as some parameters for the NAT and ice formation can be chosen. This publication explains the background of the submodel PSC and the use of the submodel with the goal to simulate realistic PSC in EMAC.

We introduce version 4 of the EQuilibrium Simplified Aerosol Model (EQSAM4), which is part of our aerosol chemistry-microphysics module (GMXe) and chemistry-climate model (EMAC). We focus on the relative humidity of deliquescence (RHD) based water uptake of atmospheric aerosols, as this is important for atmospheric chemistry and climate modeling, e.g. to calculate the aerosol optical depth (AOD). Since the main EQSAM4 applications will involve large-scale, long-term and high-resolution atmospheric chemistry-climate modeling with EMAC, computational efficiency is an important requirement. EQSAM4 parameterizes the composition and water uptake of multicomponent atmospheric aerosols by considering the gas-liquid-solid partitioning of single and mixed solutes. EQSAM4 builds on analytical, and hence CPU efficient, aerosol hygroscopic growth parameterizations to compute the aerosol liquid water content (AWC). The parameterizations are described in the companion paper (Metzger et al., 2011) and only require a compound specific coefficient νi to derive the single solute molality and the AWC for the whole range of water activity (aw). νi is pre-calculated and applied during runtime by using internal look-up tables. Here, the EQSAM4 equilibrium model is described and compared to the more explicit thermodynamic model ISORROPIA II. Both models are imbedded in EMAC/GMXe. Box model inter-comparisons, including the reference model E-AIM, and global simulations with EMAC show that gas-particle partitioning, including semi-volatiles and water, is in good agreement. A more comprehensive box model inter-comparison of EQSAM4 with EQUISOLV II is subject of the revised publication of Xu et al. (2009), i.e. Xu et al. (2011).

The response of stratospheric climate and circulation to increasing amounts of greenhouse gases (GHGs) and ozone recovery in the twenty-first century is analyzed in simulations of 11 chemistry–climate models using near-identical forcings and experimental setup. In addition to an overall global cooling of the stratosphere in the simulations (0.59 ± 0.07 K decade−1 at 10 hPa), ozone recovery causes a warming of the Southern Hemisphere polar lower stratosphere in summer with enhanced cooling above. The rate of warming correlates with the rate of ozone recovery projected by the models and, on average, changes from 0.8 to 0.48 K decade−1 at 100 hPa as the rate of recovery declines from the first to the second half of the century. In the winter northern polar lower stratosphere the increased radiative cooling from the growing abundance of GHGs is, in most models, balanced by adiabatic warming from stronger polar downwelling. In the Antarctic lower stratosphere the models simulate an increase in low temperature extremes required for polar stratospheric cloud (PSC) formation, but the positive trend is decreasing over the twenty-first century in all models. In the Arctic, none of the models simulates a statistically significant increase in Arctic PSCs throughout the twenty-first century. The subtropical jets accelerate in response to climate change and the ozone recovery produces a westward acceleration of the lower-stratospheric wind over the Antarctic during summer, though this response is sensitive to the rate of recovery projected by the models. There is a strengthening of the Brewer–Dobson circulation throughout the depth of the stratosphere, which reduces the mean age of air nearly everywhere at a rate of about 0.05 yr decade−1 in those models with this diagnostic. On average, the annual mean tropical upwelling in the lower stratosphere (∼70 hPa) increases by almost 2% decade−1, with 59% of this trend forced by the parameterized orographic gravity wave drag in the models. This is a consequence of the eastward acceleration of the subtropical jets, which increases the upward flux of (parameterized) momentum reaching the lower stratosphere in these latitudes.

A statistical framework to evaluate the performance of chemistry-climate models with respect to the interaction between meteorology and column ozone during northern hemisphere mid-winter, in particularly January, is used. Different statistical diagnostics from four chemistry-climate models (E39C, ME4C, UMUCAM, ULAQ) are compared with the ERA-40 re-analysis. First, we analyse vertical coherence in geopotential height anomalies as described by linear correlations between two different pressure levels (30 and 200 hPa) of the atmosphere. In addition, linear correlations between column ozone and geopotential height anomalies at 200 hPa are discussed to motivate a simple picture of the meteorological impacts on column ozone on interannual timescales. Secondly, we discuss characteristic spatial structures in geopotential height and column ozone anomalies as given by their first two empirical orthogonal functions. Finally, we describe the covariance patterns between reconstructed anomalies of geopotential height and column ozone. In general we find good agreement between the models with higher horizontal resolution (E39C, ME4C, UMUCAM) and ERA-40. The Pacific-North American (PNA) pattern emerges as a useful qualitative benchmark for the model performance. Models with higher horizontal resolution and high upper boundary (ME4C and UMUCAM) show good agreement with the PNA tripole derived from ERA-40 data, including the column ozone modulation over the Pacfic sector. The model with lowest horizontal resolution does not show a classic PNA pattern (ULAQ), and the model with the lowest upper boundary (E39C) does not capture the PNA related column ozone variations over the Pacific sector. Those discrepancies have to be taken into account when providing confidence intervals for climate change integrations.

Simulations from eleven coupled chemistry-climate models (CCMs) employing nearly identical forcings have been used to project the evolution of stratospheric ozone throughout the 21st century. The model-to-model agreement in projected temperature trends is good, and all CCMs predict continued, global mean cooling of the stratosphere over the next 5 decades, increasing from around 0.25 K/decade at 50 hPa to around 1 K/ decade at 1 hPa under the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenarios (SRES) A1B scenario. In general, the simulated ozone evolution is mainly determined by decreases in halogen concentrations and continued cooling of the global stratosphere due to increases in greenhouse gases (GHGs). Column ozone is projected to increase as stratospheric halogen concentrations return to 1980s levels. Because of ozone increases in the middle and upper stratosphere due to GHGinduced cooling, total ozone averaged over midlatitudes, outside the polar regions, and globally, is projected to increase to 1980 values between 2035 and 2050 and before lower stratospheric halogen amounts decrease to 1980 values. In the polar regions the CCMs simulate small temperature trends in the first and second half of the 21st century in midwinter. Differences in stratospheric inorganic chlorine (Cly) among the CCMs are key to diagnosing the intermodel differences in simulated ozone recovery, in particular in the Antarctic. It is found that there are substantial quantitative differences in the simulated Cly, with the October mean Antarctic Cly peak value varying from less than 2 ppb to over 3.5 ppb in the CCMs, and the date at which the Cly returns to 1980 values varying from before 2030 to after 2050. There is a similar variation in the timing of recovery of Antarctic springtime column ozone back to 1980 values. As most models underestimate peak Cly near 2000, ozone recovery in the Antarctic could occur even later, between 2060 and 2070. In the Arctic the column ozone increase in spring does not follow halogen decreases as closely as in the Antarctic, reaching 1980 values before Arctic halogen amounts decrease to 1980 values and before the Antarctic. None of the CCMs predict future large decreases in the Arctic column ozone. By 2100, total column ozone is projected to be substantially above 1980 values in all regions except in the tropics.

[1] Stratospheric and upper tropospheric distributions of peroxynitric acid (HO2NO2) were retrieved from limb infrared spectral measurements of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board the Environmental Satellite (ENVISAT). Single-profile precisions are estimated at 6–14 parts per trillion by volume (pptv) in the altitude range 7–17 km and 19–34 pptv from 17 to 42 km. The vertical resolution is 5 km in the upper tropospheric and stratospheric maxima. Highest stratospheric volume mixing ratios (VMRs) reaching 310 pptv at 27 km are observed at solstice conditions in subtropical latitudes and midlatitudes at the nighttime summer hemisphere, while lowest stratospheric peak VMRs as low as 38 pptv are found during polar winter near the pole. A second maximum in the upper troposphere and lower stratosphere appears from spring to the end of summer with maximum values of 80 pptv between 7 and 14 km. Retrievals based on spectroscopic line list data instead of absorption cross sections produce HO2NO2 distributions smaller by a factor of 1.5, on average. Earlier HO2NO2 measurements from balloon instruments are in good general agreement with the presented data set if the same spectroscopic data are used. Comparisons of MIPAS HO2NO2 distributions to results of the fifth-generation European Centre Hamburg general circulation model/Modular Earth Submodel System 1 (ECHAM5/MESSy1) provide agreement within 20% if near-infrared photolysis is considered. With the newly available tabulated absorption cross sections and the improved photolysis modeling, former discrepancies between HO2NO2 observations and model calculations can be considered to be largely resolved.

The mechanisms responsible for the extreme dryness of the stratosphere have been debated for decades. A key difficulty has been the lack of comprehensive models which are able to reproduce the observations. Here we examine results from the coupled lower-middle atmosphere chemistry general circulation model ECHAM5/MESSy1 together with satellite observations. Our model results match observed temperatures in the tropical lower stratosphere and realistically represent the seasonal and inter-annual variability of water vapor. The model reproduces the very low water vapor mixing ratios (below 2 ppmv) periodically observed at the tropical tropopause near 100 hPa, as well as the characteristic tape recorder signal up to about 10 hPa, providing evidence that the dehydration mechanism is well-captured. Our results confirm that the entry of tropospheric air into the tropical stratosphere is forced by large-scale wave dynamics, whereas radiative cooling regionally decelerates upwelling and can even cause downwelling. Thin cirrus forms in the cold air above cumulonimbus clouds, and the associated sedimentation of ice particles between 100 and 200 hPa reduces water mass fluxes by nearly two orders of magnitude compared to air mass fluxes. Transport into the stratosphere is supported by regional net radiative heating, to a large extent in the outer tropics. During summer very deep monsoon convection over Southeast Asia, centered over Tibet, moistens the stratosphere.

The long-term evolution of upper stratospheric ozone has been recorded by lidars and microwave radiometers within the ground-based Network for the Detection of Stratospheric Change (NDSC), and by the space-borne Solar Backscatter Ultra-Violet instruments (SBUV), Stratospheric Aerosol and Gas Experiment (SAGE), and Halogen Occultation Experiment (HALOE). Climatological mean differences between these instruments are typically smaller than 5% between 25 and 50 km. Ozone anomaly time series from all instruments, averaged from 35 to 45 km altitude, track each other very well and typically agree within 3 to 5%. SBUV seems to have a slight positive drift against the other instruments. The corresponding 1979 to 1999 period from a transient simulation by the fully coupled MAECHAM4-CHEM chemistry climate model reproduces many features of the observed anomalies. However, in the upper stratosphere the model shows too low ozone values and too negative ozone trends, probably due to an underestimation of methane and a consequent overestimation of ClO. The combination of all observational data sets provides a very consistent picture, with a long-term stability of 2% or better. Upper stratospheric ozone shows three main features: (1) a decline by 10 to 15% since 1980, due to chemical destruction by chlorine; (2) two to three year fluctuations by 5 to 10%, due to the Quasi-Biennial Oscillation (QBO); (3) an 11-year oscillation by about 5%, due to the 11-year solar cycle. The 1979 to 1997 ozone trends are larger at the southern mid-latitude station Lauder (45 S), reaching 8%/decade, compared to only about 6%/decade at Table Mountain (35 N), Haute Provence/Bordeaux (approximately equal to 45 N), and Hohenpeissenberg/Bern(approximately equal to 47 N). At Lauder, Hawaii (20 N), Table Mountain, and Haute Provence, ozone residuals after subtraction of QBO- and solar cycle effects have levelled off in recent years, or are even increasing. Assuming a turning point in January 1997, the change of trend is largest at southern mid-latitude Lauder, +11%/decade, compared to +7%/decade at northern mid-latitudes. This points to a beginning recovery of upper stratospheric ozone. However, chlorine levels are still very high and ozone will remain vulnerable. At this point the most northerly mid-latitude station, Hohenpeissenberg/Bern differs from the other stations, and shows much less clear evidence for a beginning recovery, with a change of trend in 1997 by only +3%/decade. In fact, record low upper stratospheric ozone values were observed at Hohenpeissenberg/Bern, and to a lesser degree at Table Mountain and Haute Provence, in the winters 2003/2004 and 2004/2005.

Catalytic cycles and other chemical pathways affecting ozone are normally estimated empirically in atmospheric models. In this work we have automatically quantified such processes by applying a newly developed analysis package called the Pathway Analysis Program (PAP). It used modeled chemical rates and concentrations as input. These were supplied by the Module Efficiently Calculating the Chemistry of the Atmosphere MECCA box model, itself initialized by the Free University of Berlin Climate Middle Atmosphere Model with Chemistry. We analyzed equatorial, midlatitude and high-latitude locations over 24-hour periods during spring in both hemispheres. We present results for locations in the lower stratosphere, upper stratosphere and midmesosphere. Oxygen photolysis dominated (>99%) in situ ozone production in the equatorial lower stratosphere, in the upper stratosphere and in the mesosphere. In the lower stratosphere midlatitudes the ozone smog cycle (already established in the troposphere) rivaled oxygen photolysis as an in situ ozone source in both hemispheres. However, absolute ozone production rates in midlatitudes were rather slow compared with at the equator, typically 1650 ppt ozone/day. In the equatorial lower stratosphere, five catalytic sinks were important (each contributing at least 5% to chemical ozone loss): a HOx cycle, a HOBr cycle and its HOCl analog, a water-HOx cycle and a mixed chlorine-bromine cycle. Important in midlatitudes were the HOx cycle, a NOx cycle, the HOBr cycle and the mixed chlorine-bromine cycle. In lower-stratosphere high latitudes, the chlorine dimer cycle and the mixed chlorine-bromine cycle dominated in both hemispheres. A variant on the latter, involving BrCl formation, also featured. In the upper stratosphere high latitudes (where strong negative ozone trends are observed), a nitrogen cycle, a chlorine cycle, and a mixed chlorine-nitrogen cycle were found. In the mesosphere, three closely related HOx cycles dominated ozone loss.

We report results from a multiple linear regression analysis of long-term total ozone observations (1979 to 2000, by TOMS/SBUV), of temperature reanalyses (1958 to 2000, NCEP), and of two chemistry-climate model simulations (1960 to 1999, by ECHAM4.L39(DLR)/CHEM (=E39/C), and MAECHAM4-CHEM). The model runs are transient experiments, where observed sea surface temperatures, increasing source gas concentrations (CO2, CFCs, CH4, N2O, NOx), 11-year solar cycle, volcanic aerosols and the quasi-biennial oscillation (QBO) are all accounted for. MAECHAM4-CHEM covers the atmosphere from the surface up to 0.01 hPa (≈80 km). For a proper representation of middle atmosphere (MA) dynamics, it includes a parametrization for momentum deposition by dissipating gravity wave spectra. E39/C, on the other hand, has its top layer centered at 10 hPa (≈30 km). It is targeted on processes near the tropopause, and has more levels in this region. Despite some problems, both models generally reproduce the observed amplitudes and much of the observed low-latitude patterns of the various modes of interannual variability in total ozone and lower stratospheric temperature. In most aspects MAECHAM4-CHEM performs slightly better than E39/C. MAECHAM4-CHEM overestimates the long-term decline of total ozone, whereas underestimates the decline over Antarctica and at northern mid-latitudes. The true long-term decline in winter and spring above the Arctic may be underestimated by a lack of TOMS/SBUV observations in winter, particularly in the cold 1990s. Main contributions to the observed interannual variations of total ozone and lower stratospheric temperature at 50 hPa come from a linear trend (up to -10 DU/decade at high northern latitudes, up to -40 DU/decade at high southern latitudes, and around -0.7 K/decade over much of the globe), from the intensity of the polar vortices (more than 40 DU, or 8 K peak to peak), the QBO (up to 20 DU, or 2 K peak to peak), and from tropospheric weather (up to 20 DU, or 2 K peak to peak). Smaller variations are related to the 11-year solar cycle (generally less than 15 DU, or 1 K), or to ENSO (up to 10 DU, or 1 K). These observed variations are replicated well in the simulations. Volcanic eruptions have resulted in sporadic changes (up to -30 DU, or +3 K). At low latitudes, patterns are zonally symmetric. At higher latitudes, however, strong, zonally non-symmetric signals are found close to the Aleutian Islands or south of Australia. Such asymmetric features appear in the model runs as well, but often at different longitudes than in the observations. The results point to a key role of the zonally asymmetric Aleutian (or Australian) stratospheric anti-cyclones for interannual variations at high-latitudes, and for coupling between polar vortex strength, QBO, 11-year solar cycle and ENSO., Atmospheric Chemistry and Physics, 6 (2), ISSN:1680-7375, ISSN:1680-7367

[1] The structural modulation of the Arctic Oscillation (AO) induced by a realistic enhancement of the ultraviolet (UV) radiation associated with the 11-year solar cycle is investigated with a coupled Chemistry-Climate Model. It has been found that the main features of the modulation are an eastward shift of the surface Atlantic center of action into Europe and a vertical extension into the stratosphere in solar maximum conditions. These model results are in good agreement with observational results in the North Atlantic Oscillation (NAO) centers of action. Confirmation of the modulation effect of solar activity on the NAO spatial structure by a Chemistry-Climate Model simulation gives support to the occurrence of a real solar effect on the tropospheric circulation.