A model study of the January 2006 low total ozone episode over Western Europe and comparison with ozone sonde data

Total column and stratospheric ozone levels at mid-latitudes often reveal strong fluctuations on time scales of days caused by dynamic processes. In some cases the total ozone column is distinctly reduced below climatological values. Here, a very low total ozone episode around 19 January 2006 over Western Europe is investigated when the observed total ozone column over Uccle (BE), measured by a Brewer spectrophotometer, reached a daily minimum of 200 DU, the lowest recorded value at this station. In order to investigate the mechanisms leading to the ozone minimum, the present study used data from (i) six ozone sounding stations in Western and Middle Europe, (ii) ECMWF meteorological fields, (iii) a simulation of the CLaMS model for January 2006, (iv) a multi-year run of the chemistry transport model KASIMA, and (v) a six-year run of the climate chemistry model ECHAM5/MESSy1. The ozone decrease at different heights was quantified and it was determined to what extent different transport mechanisms, and instantaneous, in-situ chemical ozone depletion contributed to the event. All three models reproduced the evolution and formation of the event. The ozone column decrease between Theta=300 and 750K was strongest at Uccle (BE) and De Bilt (NL) with 108 and 103 DU, respectively, and somewhat lower at Hohenpeissenberg (DE), Payerne (CH), Prague (CZ) and Lerwick (UK) with 85, 84, 83 and 74 DU, respectively. This analysis demonstrated that mainly the displacement of the ozone depleted polar vortex contributed to the ozone column decrease. Advection of ozone-poor low-latitude air masses was important in the UTLS region. The vertical displacement of isentropes connected with divergence of air out of the column was found to be of minor importance compared to the horizontal transport processes. Severe low total ozone episodes seem to occur when the mentioned mechanisms are superimposed. Instantaneous, in-situ chemical ozone depletion accounted for only 2+/-1% of the overall total ozone decrease at the sounding stations

HOCl chemistry in the Antarctic stratospheric vortex 2002, as observed with the Michelson interferometer for passive atmospheric sounding (MIPAS)

In the 2002 Antarctic polar vortex enhanced HOCl mixing ratios were detected by the Michelson Interferometer for Passive Atmospheric Sounding both at altitudes of around 35 km (1000K potential temperature), where HOCl abundances are ruled by gas phase chemistry and at around 18–24 km (475–625 K), which belongs to the altitude domain where heterogeneous chlorine chemistry is relevant. At altitudes of 33 to 40 km polar vortex HOCl mixing ratios were found to be around 0.14 ppbv as long as the polar vortex was intact, centered at the pole, and thus received relatively little sunlight. This is the altitude region where in midlatitudinal and tropic atmospheres peak HOCl mixing ratios significantly above 0.2 ppbv (in terms of daily mean values) are observed. After deformation and displacement of the polar vortex in the course of a major warming, ClO-rich vortex air was more exposed to sunlight, where enhanced HOx abundances led to largely increased HOCl mixing ratios (up to 0.3 ppbv), exceeding typical midlatitudinal and tropical amounts significantly. The HOCl increase was preceded by an increase of ClO. Model runs could reproduce these measurements only when the Stimpfle et al. (1979) rate constant for the reaction ClO+HO2→HOCl+O2 was used but not with the current JPL recommendation. At an altitude of 24 km, HOCl mixing ratios of up to 0.15 ppbv were detected. This HOCl enhancement, which is already visible in 18 September data, is attributed to heterogeneous chemistry, which is in agreement with observations of polar stratospheric clouds. The measurements were compared to a model run where no polar stratospheric clouds appeared during the observation period. The fact that HOCl still was produced in the model run suggests that a significant part of HOCl was generated from ClO rather than directly via heterogeneous reaction. Excess ClO, lower ClONO2 and earlier loss of HOCl in the measurements are attributed to ongoing heterogeneous chemistry which is not reproduced by the model. On 11 October, polar vortex mean daytime mixing ratios were only 0.03 ppbv

Global stratospheric hydrogen peroxide distribution from MIPAS-Envisat full resolution spectra compared to KASIMA model results

MIPAS-ENVISAT full resolution spectra were analyzed to obtain a global distribution of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) in the stratosphere. H<sub>2</sub>O<sub>2</sub> acts as reservoir gas for the HO<sub>x</sub> family (= H+OH+HO<sub>2</sub>) and thus, observations of H<sub>2</sub>O<sub>2</sub> provide a better understanding of the HO<sub>x</sub> chemistry in the atmosphere. A retrieval approach based on constrained least squares fitting was developed and applied to small dedicated spectral analysis windows with maximum H<sub>2</sub>O<sub>2</sub> information and minimum contribution of interfering gases. Due to a low signal to noise ratio in the measured spectra single profiles cannot be used for scientific interpretation and about 100 profiles have to be averaged temporally or spatially. Our retrievals of H<sub>2</sub>O<sub>2</sub> from MIPAS measurements provide meaningful results between approximately 20 and 60 km. A possible impact by the high uncertainty of the reaction rate constant for HO<sub>2</sub> + HO<sub>2</sub>→H<sub>2</sub>O<sub>2</sub> + O<sub>2</sub> in our 3D-CTM KASIMA is discussed. We find best agreement between model and observations for applying rate constants according to Christensen et al. (2002) however, a mismatch in vertical profile shape remains. The observations were compared to the model results of KASIMA focusing on low to mid latitudes. Good agreement in spatial distribution and in temporal evolution was found. Highest vmr of H<sub>2</sub>O<sub>2</sub> in the stratosphere were observed and modeled in low latitudes shortly after equinox at about 30 km. The modelled diurnal cycle with lowest vmr shortly after sunrise and highest vmr in the afternoon is confirmed by the MIPAS observations

From climatological to small-scale applications: simulating water isotopologues with ICON-ART-Iso (version 2.3)

We present the new isotope-enabled model ICON-ART-Iso. The physics package of the global ICOsahedral Nonhydrostatic (ICON) modeling framework has been extended to simulate passive moisture tracers and the stable isotopologues HDO and H182O. The extension builds on the infrastructure provided by ICON-ART, which allows for high flexibility with respect to the number of related water tracers that are simulated. The physics of isotopologue fractionation follow the model COSMOiso. We first present a detailed description of the physics of fractionation that have been implemented in the model. The model is then evaluated on a range of temporal scales by comparing with measurements of precipitation and vapor. A multi-annual simulation is compared to observations of the isotopologues in precipitation taken from the station network GNIP (Global Network for Isotopes in Precipitation). ICON-ART-Iso is able to simulate the main features of the seasonal cycles in δD and δ18O as observed at the GNIP stations. In a comparison with IASI satellite retrievals, the seasonal and daily cycles in the isotopologue content of vapor are examined for different regions in the free troposphere. On a small spatial and temporal scale, ICON-ART-Iso is used to simulate the period of two flights of the IAGOS-CARIBIC aircraft in September 2010, which sampled air in the tropopause region influenced by Hurricane Igor. The general features of this sample as well as those of all tropical data available from IAGOS-CARIBIC are captured by the model. The study demonstrates that ICON-ART-Iso is a flexible tool to analyze the water cycle of ICON. It is capable of simulating tagged water as well as the isotopologues HDO and H182

Diurnal variations of reactive chlorine and nitrogen oxides observed by MIPAS-B inside the January 2010 Arctic vortex

The winter 2009/2010 was characterized by a strong Arctic vortex with extremely cold mid-winter temperatures in the lower stratosphere associated with an intense activation of reactive chlorine compounds (ClOx) from reservoir species. Stratospheric limb emission spectra were recorded during a flight of the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 24 January 2010 inside the Arctic vortex. Several fast limb sequences of spectra (in time steps of about 10 min) were measured from nighttime photochemical equilibrium to local noon allowing the retrieval of chlorine- and nitrogen-containing species which change rapidly their concentration around the terminator between night and day. Mixing ratios of species like ClO, NO2, and N2O5 show significant changes around sunrise, which are temporally delayed due to polar stratospheric clouds reducing the direct radiative flux from the sun. ClO variations were derived for the first time from MIPAS-B spectra. Daytime ClO values of up to 1.6 ppbv are visible in a broad chlorine activated layer below 26 km correlated with low values (below 0.1 ppbv) of the chlorine reservoir species ClONO2. Observations are compared and discussed with calculations performed with the 3-dimensional Chemistry Climate Model EMAC (ECHAM5/MESSy Atmospheric Chemistry). Mixing ratios of the species ClO, NO2, and N2O5 are well reproduced by the model during night and noon. However, the onset of ClO production and NO2 loss around the terminator in the model is not consistent with the measurements. The MIPAS-B observations along with Tropospheric Ultraviolet-Visible (TUV) radiation model calculations suggest that polar stratospheric clouds lead to a delayed start followed by a faster increase of the photodissoziation of ClOOCl and NO2 near the morning terminator since stratospheric clouds alter the direct and the diffuse flux of solar radiation. These effects are not considered in the EMAC model simulations which assume a cloudless atmosphere