ALBERT

Description: The first tropospheric and stratospheric (4 to 33 km) BrO profile is presented for the inner tropics derived from balloon-borne DOAS (Differential Optical Absorption Spectroscopy) measurements. In combination with photochemical modelling, total stratospheric inorganic bromine (Bry) is deduced to be (21.5±2.5) ppt in 4.5-year-old air, probed in 2005. We derive a total contribution of (5.2±2.5) ppt from brominated very short-lived substances and inorganic product gases to stratospheric Bry. Tropospheric BrO was found to be

Description: We have used total ozone columns and vertical profiles of ozone and temperature from 11 coupled Chemistry-Climate Models (CCMs) to project future solar ultraviolet radiation levels at the surface in the 21st century. The CCM simulations are used as input to a radiative transfer model for the simulation of the corresponding future UV irradiance levels under cloud free conditions, presented here as time series of monthly erythemal irradiance received at the surface during local noon covering the period 1960 to 2100. Starting from the first decade of the 21st century, the surface erythemal irradiance decreases globally as a result of the projected ozone recovery, at rates which are larger in the first half of the 21st century, compared to the period up to 2100. The magnitude of these decreases varies with latitude and is more pronounced at areas where ozone has been depleted most considerably after 1980. Over midlatitudes surface erythemal irradiance decreases between 5 and 15% by 2100 relative to 2000, while at the southern high latitudes these changes are twice as much. Climate change may affect future cloudiness, surface reflectivity and tropospheric aerosol loading, the effects of which are not included in this study. Therefore, the actual changes in future UV radiation are likely to change accordingly in the areas affected.

Description: We have studied the impact of the recently established reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM). Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT). Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and southern hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. Mean global decreases in OH are around 13% which leads to a increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and southern hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.

Description: Chlorine dioxide, OClO, column amounts retrieved from measurements of the SCIAMACHY satellite instrument are presented and validated by comparison with simultaneous ground-based DOAS observations. In addition, the measurements are compared to model calculations taking into account the photochemical change along the light path. Although OClO does not participate directly in the destruction of ozone, its accurate measurement as well as modelling is crucial to understand the highly perturbed chlorine chemistry in the polar vortices. SCIAMACHY OClO slant columns retrieved during spring 2005 have been quantitatively validated by comparison with slant columns retrieved from measurements made in Ny-Ålesund (79° N, 12° E), Summit (73° N, 38° W) and Bremen (53° N, 9° E). Overall, good agreement is found. OClO slant column densities modelled with a set of stacked box models and considering the light path through the atmosphere are also included in this comparison. The model predictions differ significantly from the measured quantities. OClO amounts are underestimated for conditions of strong chlorine activation and at large solar zenith angles. Sensitivity studies for several parameters in the stacked box model have been performed and it is inferred that using the chemistry known to date, the observed OClO cannot be adequately reproduced within the range of uncertainties given for the various model parameters.

Description: The first study of the global atmospheric distribution of carbon tetrachloride (CCl4), as a function of altitude and latitude, was performed using solar occultation measurements obtained by the Atmospheric Chemistry Experiment (ACE) mission using Fourier transform spectroscopy. A total of 8703 profile measurements were used in the study taken between February 2004 and August 2007. The zonal distribution of carbon tetrachloride displays a slight hemispheric asymmetry and decreasing concentration with increasing altitude at all latitudes. Maximum carbon tetrachloride concentrations are situated below 10 km in altitude with VMR (Volume Mixing Ratio) values of 100–130 ppt (parts per trillion). The highest concentrations are located about the equator and at mid-latitudes, particularly for latitudes in heavily industrialised regions (20–45° N), with values declining towards the poles. Global distributions obtained from ACE were compared with predictions from three chemistry transport models. The ACE dataset gives unique global and temporal coverage of carbon tetrachloride and its transport through the atmosphere. An estimated lifetime for carbon tetrachloride of 34±5 years was determined through correlation with CFC-11.

Description: The SLIMCAT three-dimensional chemical transport model (CTM) is used to infer chemical ozone loss from Polar Ozone and Aerosol Measurement (POAM) III observations of stratospheric ozone during the Arctic winter of 2002-2003. Inferring chemical ozone loss from satellite data requires quantifying ozone variations due to dynamical processes. To accomplish this, the SLIMCAT model was run in a "passive" mode from early December until the middle of March. In these runs, ozone is treated as an inert, dynamical tracer. Chemical ozone loss is inferred by subtracting the model passive ozone, evaluated at the time and location of the POAM observations, from the POAM measurements themselves. This "CTM Passive Subtraction" technique relies on accurate initialization of the CTM and a realistic description of vertical/horizontal transport, both of which are explored in this work. The analysis suggests that chemical ozone loss during the 2002-2003 winter began in late December. This loss followed a prolonged period in which many polar stratospheric clouds were detected, and during which vortex air had been transported to sunlit latitudes. A series of stratospheric warming events starting in January hindered chemical ozone loss later in the winter of 2003. Nevertheless, by 15 March, the final date of the analysis, ozone loss maximized at 425K at a value of about 1.2ppmv, a moderate amount of loss compared to loss during the unusually cold winters in the late-1990s. SLIMCAT was also run with a detailed stratospheric chemistry scheme to obtain the model-predicted loss. The SLIMCAT model simulation also shows a maximum ozone loss of 1.2ppmv at 425K, and the morphology of the loss calculated by SLIMCAT was similar to that inferred from the POAM data. These results from the recently updated version of SLIMCAT therefore give a much better quantitative description of polar chemical ozone loss than older versions of the same model. Both the inferred and modeled loss calculations show the early destruction in late December and the region of maximum loss descending in altitude through the remainder of the winter and early spring.

Description: We have used the SLIMCAT 3-D off-line chemical transport model (CTM) to quantify the Arctic chemical ozone loss in the year 2002/2003 and compare it with similar calculations for the winters 1999/2000 and 2003/2004. Recent changes to the CTM have improved the model's ability to reproduce polar chemical and dynamical processes. The updated CTM uses σ-θ as a vertical coordinate which allows it to extend down to the surface. The CTM has a detailed stratospheric chemistry scheme and now includes a simple NAT-based denitrification scheme in the stratosphere. In the model runs presented here the model was forced by ECMWF ERA40 and operational analyses. The model used 24 levels extending from the surface to ~55km and a horizontal resolution of either 7.5° x 7.5° or 2.8° x 2.8°. Two different radiation schemes, MIDRAD and the CCM scheme, were used to diagnose the vertical motion in the stratosphere. Based on tracer observations from balloons and aircraft, the more sophisticated CCM scheme gives a better representation of the vertical transport in this model which includes the troposphere. The higher resolution model generally produces larger chemical O3 depletion, which agrees better with observations. The CTM results show that very early chemical ozone loss occurred in December 2002 due to extremely low temperatures and early chlorine activation in the lower stratosphere. Thus, chemical loss in this winter started earlier than in the other two winters studied here. In 2002/2003 the local polar ozone loss in the lower stratosphere was ~40% before the stratospheric final warming. Larger ozone loss occurred in the cold year 1999/2000 which had a persistently cold and stable vortex during most of the winter. For this winter the current model, at a resolution of 2.8° x 2.8°, can reproduce the observed loss of over 70% locally. In the warm and more disturbed winter 2003/2004 the chemical O3 loss was generally much smaller, except above 620K where large losses occurred due to a period of very low minimum temperatures at these altitudes.

Description: We have studied the impact of the recently observed reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM). Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT). Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and Southern Hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. The mean global decrease in OH is around 13%, which is very large compared to the impact that typical photochemical revisions have on this modelled quantity. This OH decrease leads to an increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and Southern Hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.

Description: Bromine compounds play an important role in the depletion of stratospheric ozone. We have calculated the changes in stratospheric ozone in response to changes in the halogen loading over the past decades, using a two-dimensional (latitude/height) model constrained by source gas mixing ratios at the surface. Model calculations of the decrease of total column ozone since 1980 agree reasonably well with observed ozone trends, in particular when the contribution from very short-lived bromine compounds is included. Model calculations with bromine source gas mixing ratios fixed at 1959 levels, corresponding approximately to a situation with no anthropogenic bromine emissions, show an ozone column reduction between 1980 and 2005 at Northern Hemisphere mid-latitudes of only ≈55% compared to a model run including all halogen source gases. In this sense anthropogenic bromine emissions are responsible for ≈45% of the model estimated column ozone loss at Northern Hemisphere mid-latitudes. However, since a large fraction of the bromine induced ozone loss is due to the combined BrO/ClO catalytic cycle, the effect of bromine would have been smaller in the absence of anthropogenic chlorine emissions. The chemical efficiency of bromine relative to chlorine for global total ozone depletion from our model calculations, expressed by the so called α-factor, is 64 on an annual average. This value is much higher than previously published results. Updates in reaction rate constants can explain only part of the differences in α. The inclusion of bromine from very short-lived source gases has only a minor effect on the global mean α-factor.

Description: We use the new GLOMAP model of global aerosol microphysics to investigate the sensitivity of modelled sulfate and sea salt aerosol properties to uncertainties in the driving microphysical processes and compare these uncertainties with those associated with aerosol and precursor gas emissions. Overall, we conclude that uncertainties in microphysical processes have a larger effect on global sulfate and sea salt derived condensation nuclei (CN) and cloud condensation nuclei (CCN) concentrations than uncertainties in present-day sulfur emissions. Our simulations suggest that uncertainties in predicted sulfate and sea salt CCN abundances due to poorly constrained microphysical processes are likely to be of a similar magnitude to long-term changes in sulfate and sea salt CCN due to changes in anthropogenic emissions. A microphysical treatment of the global sulfate aerosol allows the uncertainty in climate-relevant aerosol properties to be attributed to specific processes in a way that has not been possible with simpler aerosol schemes. In particular we conclude that: (1) changes in the binary H2SO4-H2O nucleation rate and condensation rate of gaseous H2SO4 cause a shift in the vertical location of the upper tropospheric CN layer by as much as 3 km, while the shape of the CN profile is essentially pre-served (2) uncertainties in the binary H2SO4-H2O nucleation rate have a relatively insignificant effect on marine boundary layer (MBL) aerosol properties; (3) emitting a fraction of anthropogenic SO2 as particulates (to represent production of sulfate particles in power plant plumes below the scale of the model grid (which is of the order of 300 km)) has the potential to change the global mean MBL sulfate-derived CN concentrations by up to 72%, and changes of up to a factor 20 can occur in polluted continental regions; (4) predicted global mean MBL sulfate and sea salt CCN concentrations change by 10 to 60% when several microphysical processes are changed within reasonable uncertainty ranges; (5) sulfate and sea salt derived CCN concentrations are particularly sensitive to primary particle emissions, with global mean MBL sulfate and sea salt CCN changing by up to 27% and local concentrations over continental regions changing by more than 100% when the percentage of anthropogenic SO2 emitted as particulates is changed from 0 to 5%; (6) large changes in sea spray flux have insignificant effects on global sulfate aerosol except when the mass accommodation coefficient of sulfuric acid on the salt particles is set unrealistically low.