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Heterogeneous conversion of NO2 and NO on HNO3 treated soot surfaces: atmospheric implications

In the present study, the heterogeneous conversion of nitrogen oxide (NO) and nitrogen dioxide (NO2) was studied at atmospheric humidity levels on flame soot surfaces treated with gaseous nitric acid (HNO3). In addition, the heterogeneous reaction of HNO3 on soot was investigated at atmospheric humidity. For the treatment of soot by pure HNO3 only reversible uptake with a surface coverage of ~1-2x1014 HNO3 cm-2 was observed for HNO3 mixing ratios in the range 250-800ppbv. Only for higher HNO3 mixing ratios of >800ppbv the formation of NO and NO2 was observed. The results were not affected by the addition of NO. In none of the experiments with HNO3 the formation of nitrous acid (HONO) was observed. For HNO3 mixing ratios <600ppbv the upper limit yields for HONO, NO2 and NO were found to be <0.2%, <0.5% and <1%, respectively. Compared to untreated soot, the product formation of the reaction of NO2 with soot was not significantly affected when the soot surface was treated with gaseous HNO3 prior to the experiment. Only for high surface coverage of HNO3 the formation of HONO was suppressed in the initial phase of the reaction, probably caused by the blocking of active sites by adsorbed HNO3. Under the assumption that the experimental findings for the used model flame soot can be extrapolated to atmospheric soot particles, the results show that the reactions of HNO3 and HNO3+NO on soot surfaces are unimportant for a "renoxification" of the atmosphere and do not represent an atmospheric HONO source. In addition, the integrated HONO yield of ca. 1014cm-2 in the reaction of NO2 with soot is not significantly influenced by simulated atmospheric processing of the soot surface by HNO3, and is still too small to explain HONO formation in the atmosphere.
Intercomparison between Lagrangian and Eulerian simulations of the development of mid-latitude streamers as observed by CRISTA

During the CRISTA-1 mission three pronounced fingerlike structures reaching from the lower latitudes to the mid-latitudes, so-called streamers, were observed in the measurements of several trace gases in early November 1994. A simulation of these streamers in previous studies employing the KASIMA (Karlsruhe Simulation Model of the Middle Atmosphere) and ROSE (Research on Ozone in the Stratosphere and its Evolution) model, both being Eulerian models, show that their formation is due to adiabatic transport processes. Here, the impact of mixing on the development of these streamers is investigated. These streamers were simulated with the CLaMS model (Chemical Lagrangian Model of the Stratosphere), a Lagrangian model, using N2O as long-lived tracer. Using several different initialisations the results were compared to the KASIMA simulations and CRISTA (Cryogenic Infrared Spectrometer and Telescope for the Atmosphere) observations. Further, since the KASIMA model was employed to derive a 9-year climatology, the quality of the reproduction of streamers from such a study was tested by the comparison of the KASIMA results with CLaMS and CRISTA. The streamers are reproduced well for the Northern Hemisphere in the simulations of CLaMS and KASIMA for the 6 November 1994. However, in the CLaMS simulation a stronger filamentation is found while larger discrepancies between KASIMA and CRISTA were found especially for the Southern Hemisphere. Further, compared to the CRISTA observations the mixing ratios of N2O are in general underestimated in the KASIMA simulations. An improvement of the simulations with KASIMA was obtained for a simulation time according to the length of the CLaMS simulation. To quantify the differences between the simulations with CLaMS and KASIMA, and the CRISTA observations, the probability density function technique (PDF) is used to interpret the tracer distributions. While in the PDF of the KASIMA simulation the small scale structures observed by CRISTA are smoothed out due to the numerical diffusion in the model, the PDFs derived from CRISTA observations can be reproduced by CLaMS by optimising the mixing parameterisation. Further, this procedure gives information on small-scale variabilities not resolved by the CRISTA observations.
Vortex-averaged Arctic ozone depletion in the winter 2002/2003

A total ozone depletion of 68±7 Dobson units between 380 and 525K from 10 December 2002 to 10 March 2003 is derived from ozone sonde data by the vortex-average method, taking into account both diabatic descent of the air masses and transport of air into the vortex. When the vortex is divided into three equal-area regions, the results are 85±9DU for the collar region (closest to the edge), 52±5DU for the vortex centre and 68±7DU for the middle region in between centre and collar. Our results compare well with other studies: We find good agreement with ozone loss deduced from SAOZ data, with results inferred from POAM III observations and with results from tracer-tracer correlations using HF as the long-lived tracer. We find a higher ozone loss than that deduced by tracer-tracer correlations using CH4. We have made a careful comparison with Match results: The results were recalculated using a common time period, vortex edge definition and height interval. The two methods generally compare very well, except at the 475K level which exhibits an unexplained discrepancy.
Climatological features of stratospheric streamers in the FUB-CMAM with increased horizontal resolution

The purpose of this study is to investigate horizontal transport processes in the winter stratosphere using data with a resolution relevant for chemistry and climate modeling. For this reason the Freie Universität Berlin Climate Middle Atmosphere Model (FUB-CMAM) with its model top at 83 km altitude, increased horizontal resolution T42 and the semi-Lagrangian transport scheme for advecting passive tracers is used. A new approach of this paper is the classification of specific transport phenomena within the stratosphere into tropical-subtropical streamers (e.g. Offermann et al., 1999) and polar vortex extrusions hereafter called polar vortex streamers. To investigate the role played by these large-scale structures on the inter-annual and seasonal variability of transport processes in northern mid-latitudes, the global occurrence of such streamers was calculated based on a 10-year model climatology, concentrating on the existence of the Arctic polar vortex. For the identification and counting of streamers, the new method of zonal anomaly was chosen. The analysis of the months October-May yielded a maximum occurrence of tropical-subtropical streamers during Arctic winter and spring in the middle and upper stratosphere. Synoptic maps revealed highest intensities in the subtropics over East Asia with a secondary maximum over the Atlantic in the northern hemisphere. Furthermore, tropical-subtropical streamers exhibited a higher occurrence than polar vortex streamers, indicating that the subtropical barrier is more permeable than the polar vortex barrier (edge) in the model, which is in good correspondence with observations (e.g. Plumb, 2002; Neu et al., 2003). Interesting for the total ozone decrease in mid-latitudes is the consideration of the lower stratosphere for tropical-subtropical streamers and the stratosphere above ~20 km altitude for polar vortex streamers, where strongest ozone depletion is observed at polar latitudes (WMO, 2003). In the lower stratosphere the FUB-CMAM simulated a climatological maximum of 10% occurrence of tropical-subtropical streamers over East-Asia/West Pacific and the Atlantic during early- and mid-winter. The results of this paper demonstrate that stratospheric streamers e.g. large-scale, tongue-like structures transporting tropical-subtropical and polar vortex air masses into mid-latitudes occur frequently during Arctic winter. They can therefore play a significant role on the strength and variability of the observed total ozone decrease at mid-latitudes and should not be neglected in future climate change studies.
Technical Note: Evaporation of polar stratospheric cloud particles, in situ, in a heated inlet

In December 2001 and 2002 in situ aerosol measurements were made from balloon-borne platforms within polar stratospheric clouds (PSC) which contained particles of supercooled ternary solution (STS), nitric acid trihydrate (NAT) and ice. Particle size and number concentrations were measured with two optical particle counters. One of these included an ~80cm inlet heated to K to evaporate the PSC particles and thus to obtain measurements, within PSCs, of the size distribution of the particles upon which the PSCs condensed. These measurements are compared to models, described here, that calculate the evaporation of PSC particles at and for an inlet transition time of about 0.1s. The modeled evaporation for STS agrees well with the measurements. For NAT the modeled evaporation is less than the evaporation measured. The primary uncertainty concerns the phase and morphology of NAT particles as they are brought to temperatures >50K above equilibrium temperatures for NAT at stratospheric partial pressures. The slow evaporation of NAT in heated inlets could be used to identify a small NAT component within a mixed phase PSC dominated by STS.
An evaluation of the performance of chemistry transport models - Part 2: Detailed comparison with two selected campaigns

This is the second part of a rigorous model evaluation study involving five global Chemistry-Transport and two Chemistry-Climate Models operated by different groups in Europe. Simulated trace gas fields were interpolated to the exact times and positions of the observations to account for the actual weather conditions and hence for the specific histories of the sampled air masses. In this part of the study we focus on a detailed comparison with two selected campaigns, PEM-Tropics A and SONEX, contrasting the clean environment of the tropical Pacific with the more polluted North Atlantic region. The study highlights the different strengths and weaknesses of the models in accurately simulating key processes in the UT/LS region including stratosphere-troposphere-exchange, rapid convective transport, lightning emissions, radical chemistry and ozone production. Model simulated Radon, which was used as an idealized tracer for continental influence, was occasionally much better correlated with measured CO than simulated CO pointing towards deficiencies in the used biomass burning emission fields. The abundance and variability of HOx radicals is in general well represented in the models as inferred directly from the comparison with measured OH and HO2 and indirectly from the comparison with hydrogen peroxide concentrations. Components of the NOy family such as PAN, HNO3 and NO were found to compare less favorably. Interestingly, models showing good agreement with observations in the case of PEM-Tropics A often failed in the case of SONEX and vice versa. A better description of NOx and NOy emissions, chemistry and sinks is thought to be key to future model improvements with respect to the representation of chemistry in the UT/LS region.
Subtropical trace gas profiles determined by ground-based FTIR spectroscopy at Izaña (28° N, 16° W): Five-year record, error analysis, and comparison with 3-D CTMs

Within the framework of the NDSC (Network for the Detection of Stratospheric Change) ground-based FTIR solar absorption spectra have been routinely recorded at Izaña Observatory (28° N, 16° W) on Tenerife Island since March 1999. By analyzing the shape of the absorption lines, and their different temperature sensitivities, the vertical distribution of the absorbers can be retrieved. Unique time series of subtropical profiles of O3, HCl, HF, N2O, and CH4 are presented. The effects of both dynamical and chemical annually varying trace gas cycles can be seen in the retrieved profiles. These include enhanced upwelling and photochemistry in summer and a more disturbed atmosphere in winter, which are typical of the subtropical stratosphere. A detailed error analysis has been performed for each profile. The output from two different three-dimensional (3-D) chemical transport models (CTMs), which are forced by ECMWF analyses, are compared to the measured profiles. Both models agree well with the measurements in tracking abrupt variations in the atmospheric structure, e.g. due to tropical streamers, in particular for the lower stratosphere. Simulated and measured profiles also reflect similar dynamical and chemical annual cycles. However, the differences between their mixing ratios clearly exceed the error bars estimated for the measured profiles. Possible reasons for this are discussed.
Comparison and evaluation of modelled and GOME measurement derived tropospheric NO2 columns over Western and Eastern Europe

We present the results of a first comparison of the tropospheric NO2 column amounts derived from the measurements of the Global Ozone Monitoring Experiment (GOME) with the simulated data from a European scale chemistry transport model (CTM) which is distinct from existing global scale CTMs in higher horizontal resolution and more detailed description of the boundary layer processes and emissions. We employ, on the one hand, the newly developed extended version of the CHIMERE CTM, which covers both Western and Eastern Europe, and, on the other hand, the most recent version (Version 2) of GOME measurement based data-products, developed at the University of Bremen. We evaluate our model with the data from ground based monitoring of ozone and verify that it has a sufficiently high level of performance, which is expected for a state-of-the-art continental scale CTM. The major focus of the study is on a systematic statistical analysis and a comparison of spatial variability of the tropospheric NO2 columns simulated with CHIMERE and derived from GOME measurements. The analysis is performed separately for Western and Eastern Europe using the data for summer months of 1997 and 2001. In this way, we obtain useful information on the nature and magnitudes of uncertainties of spatial distributions of the considered data. Specifically, for Western Europe, it is found that the uncertainties of NO2 columns from GOME and CHIMERE are predominantly of the multiplicative character, and that the mean relative random (multiplicative) errors of the GOME measurement derived and simulated data averaged over the summer seasons considered do not exceed 23% and 32%, respectively. The mean absolute (additive) errors of both kinds of the data are estimated to be less than 3x1014mol/cm2. In Eastern Europe, the uncertainties have more complex character, and the separation between their multiplicative and additive parts is not sufficiently unambiguous. It is found, however, that the total random errors of NO2 columns from both GOME and CHIMERE over Eastern Europe are not, on the average, larger than the errors of the NO2 columns with similar magnitudes over Western Europe.
Model-aided radiometric determination of photolysis frequencies in a sunlit atmosphere simulation chamber

In this work diurnal and seasonal variations of mean photolysis frequencies for the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich are calculated. SAPHIR has a complex construction with UV permeable teflon walls allowing natural sunlight to enter the reactor volume. The calculations are based on external measurements of solar spectral actinic flux and a model considering the time-dependent impact of shadows from construction elements as well as the influence of the teflon walls. Overcast and clear-sky conditions are treated in a consistent way and different assumptions concerning diffuse sky radiance distributions are tested. Radiometric measurements inside the chamber are used for an inspection of model predictions. Under overcast conditions we obtain fractions of 0.74 and 0.67 of external values for photolysis frequencies j(NO2) (NO2+hν→NO+O(3P)) and j(O1D) (O3+hν→O2+O(1D)), respectively. On a clear sky summer day these values are time-dependent within ranges 0.65-0.86 and 0.60-0.73, for j(NO2) and j(O1D), respectively. A succeeding paper (Bohn et al., 2004) is dealing with an on-road test of the model approach by comparison with photolysis frequencies from chemical actinometry experiments within SAPHIR.
Transfer of organic Br and Cl from the Biosphere to the Atmosphere during the Cretaceous/Tertiary Impact: Implications for the stratospheric Ozone Layer

Following the Cretaceous/Tertiary (K/T) meteoritic impact some 65Myr ago, large portions of aboveground terrestrial biomass were burned. As a result, large amounts of various trace gases were injected to the atmosphere, inducing a wide range of effects on climate and ecosystems. Here, it is commented on the previously unaccounted for emission to the atmosphere of methyl bromide (CH3Br) and methyl chloride (CH3Cl) from extensive biomass burning that followed the impact. Based on reported biomass burning emission rates of the above organohalogens relative to CO2, it is estimated that their emissions from global fires resulted in tropospheric mixing ratios of around 20-65.8ppbv organic Cl and 110-390pptv organic Br. The above calculated mixing ratios of organic chlorine and bromine are more than an order of magnitude greater than their present, anthropogenically perturbed level and, although the ocean ultimately might absorb them, we argue here that they could still remain in the atmosphere for many years, and a substantial fraction could be transported to the stratosphere, thus substantially affecting the ozone layer. This would have led to very serious increases in short wavelength UV radiation reaching the lowermost atmosphere.