Abstract. During several balloon flights inside the Arctic polar vortex in early 2003, unusual trace gas distributions were observed, which indicate a strong influence of mesospheric air in the stratosphere. The tuneable diode laser (TDL) instrument SPIRALE (Spectroscopie Infra-Rouge par Absorption de Lasers Embarqués) measured unusually high CO values (up to 600 ppb) on 27 January at about 30 km altitude. The cryosampler BONBON sampled air masses with very high molecular Hydrogen, extremely low SF 6 and enhanced CO values on 6 March at about 25 km altitude. Finally, the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) Fourier Transform Infra-Red (FTIR) spectrometer showed NO y values which are significantly higher than NO y * (the NO y derived from a correlation between N 2 O and NO y under undisturbed conditions), on 21 and 22 March in a layer centred at 22 km altitude. Thus, the mesospheric air seems to have been present in a layer descending from about 30 km in late January to 25 km altitude in early March and about 22 km altitude on 20 March. We present corroborating evidence from a model study using the KASIMA (KArlsruhe SImulation model of the Middle Atmosphere) model that also shows a layer of mesospheric air, which descended into the stratosphere in November and early December 2002, before the minor warming which occurred in late December 2002 lead to a descent of upper stratospheric air, cutting off a layer in which mesospheric air is present. This layer then descended inside the vortex over the course of the winter. The same feature is found in trajectory calculations, based on a large number of trajectories started in the vicinity of the observations on 6 March. Based on the difference between the mean age derived from SF 6 (which has an irreversible mesoCorrespondence to: A. Engel (an.engel@meteor.uni-frankfurt.de) spheric loss) and from CO 2 (whose mesospheric loss is much smaller and reversible) we estimate that the fraction of mesospheric air in the layer observed on 6 March, must have been somewhere between 35% and 100%.

Ozone loss in the lower and middle stratosphere in spring and summer, in particular over polar regions, is driven mainly by halogens and nitrogen oxides (NOx). Whereas the stratospheric chlorine levels are expected to decrease in the future, the role of NOx for the O3 budget in a changing climate is not well quantified. Here we combine satellite measurements and model simulations to diagnose the accumulated O3 loss during winter and spring 2002–2003 in the Arctic polar stratosphere. We show that in a winter stratosphere strongly disturbed by warmings, O3 loss processes driven by halogens and NOx can significantly overlap within the polar column and become comparable in magnitude even if a significant, halogen‐induced O3 loss has occurred. Whereas, until the beginning of March 2003, polar column O3 loss was mainly caused by the halogen chemistry within the vortex at an altitude around 18 km, the chemical O3 destruction in March and April was dominated by the NOx chemistry in O3‐rich air masses transported from the subtropics and mixed with the polar air above the region affected by the halogens. This NOx‐related O3 loss started around mid‐December 2002 in subtropical air masses above 30 km that moved poleward after the major warming in January, descended to 22 km with an increasing magnitude of O3 loss and reached surprisingly high values of up to 50% local loss around the end of April. To some extent, the NOx‐driven O3 loss was enhanced by mesospheric air trapped in the vortex at the beginning of the winter as a layer of few km in the vertical and transported downward within the vortex. The effect of NOx transported from the subtropics dominated the O3 loss processes in the polar stratosphere in spring 2003, both relative to the effect of the halogens and relative to the contribution of the mesospheric NOx sources. A comparison with the 1999/2000 Arctic winter and with the Antarctic vortex split event in 2002 shows that wave events triggered by stratospheric warmings may significantly enhance O3 loss driven by NOx when O3‐ and NOx‐rich air masses from the subtropics are transported poleward and are mixed with the vortex air.

Published by Copernicus Publications on behalf of the European Geosciences Union. Abstract. The Atmospheric Chemistry Experiment (ACE) satellite was launched on 12 August 2003. Its two instruments measure vertical profiles of over 30 atmospheric trace gases by analyzing solar occultation spectra in the ultraviolet/visible and infrared wavelength regions. The reservoir gases HNO 3 , ClONO 2 , and N 2 O 5 are three of the key species provided by the primary instrument, the ACE Fourier Transform Spectrometer (ACE-FTS). This paper describes the ACE-FTS version 2.2 data products, including the N 2 O 5 update, for the three species and presents validation comparisons with available observations. We have compared volume mixing ratio (VMR) profiles of HNO 3 , ClONO 2 , and N 2 O 5 with measurements by other satellite instruments (SMR, MLS, MIPAS), aircraft measurements (ASUR), and single balloon-flights (SPIRALE, FIRS-2). Partial columns of HNO 3 and ClONO 2 were also compared with measurements by ground-based Fourier Transform Infrared (FTIR) spectrometers. Overall the quality of the ACE-FTS v2.2 HNO 3 VMR profiles is good from 18 to 35 km. For the statistical satellite comparisons, the mean absolute differences are generally within ±1 ppbv (±20%) from 18 to 35 km. For MI-PAS and MLS comparisons only, mean relative differences lie within ±10% between 10 and 36 km. ACE-FTS HNO 3 partial columns (∼15-30 km) show a slight negative bias of −1.3% relative to the ground-based FTIRs at latitudes ranging from 77.8 • S-76.5 • N. Good agreement between ACE-FTS ClONO 2 and MIPAS, using the Institut für Meteorologie und Klimaforschung and Instituto de Astrofísica de Andalucía (IMK-IAA) data processor is seen. Mean absolute differences are typically within ±0.01 ppbv between 16 and 27 km and less than +0.09 ppbv between 27 and 34 km. The ClONO 2 partial column comparisons show varying degrees of agreement, depending on the location and the quality of the FTIR measurements. Good agreement was found for the comparisons with the midlatitude Jungfraujoch partial columns for which the mean relative difference is 4.7%. ACE-FTS N 2 O 5 has a low bias relative to MIPAS IMK-IAA, reaching −0.25 ppbv at the altitude of the N 2 O 5 maximum (around 30 km). Mean absolute differences at lower altitudes (16-27 km) are typically −0.05 ppbv for MIPAS nighttime and ±0.02 ppbv for MIPAS daytime measurements.

Abstract. Vertical profiles of NO 2 and NO have been obtained from solar occultation measurements by the Atmospheric Chemistry Experiment (ACE), using an infrared Fourier Transform Spectrometer (ACE-FTS) and (for NO 2 ) an ultraviolet-visible-near-infrared spectrometer, MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation). In this paper, the quality of the ACE-FTS version 2.2 NO 2 and NO and the MAESTRO version 1.2 NO 2 data are assessed using other solar occultation measurements (HALOE, SAGE II, SAGE III, POAM III, SCIAMACHY), stellar occultation measurements (GOMOS), limb measurements (MIPAS, OSIRIS), nadir measurements (SCIA-MACHY), balloon-borne measurements (SPIRALE, SAOZ) and ground-based measurements (UV-VIS, FTIR). Time differences between the comparison measurements were reduced using either a tight coincidence criterion, or where possible, chemical box models. ACE-FTS NO 2 and NO and the MAESTRO NO 2 are generally consistent with the correlative data. The ACE-FTS and MAESTRO NO 2 volume mixing ratio (VMR) profiles agree with the profiles from other satellite data sets to within about 20% between 25 and 40 km, with the exception of MIPAS ESA (for ACE-FTS) and SAGE II (for ACE-FTS (sunrise) and MAESTRO) and suggest a negative bias between 23 and 40 km of about 10%. MAESTRO reports larger VMR values than the ACE-FTS. In comparisons with HALOE, ACE-FTS NO VMRs typically (on average) agree to ±8% from 22 to 64 km and to +10% from 93 to 105 km, with maxima of 21% and 36%, respectively. Partial column comparisons for NO 2 show that there is quite good agreement between the ACE instruments and the FTIRs, with a mean difference of +7.3% for ACE-FTS and +12.8% for MAESTRO.

The balloonborne SPIRALE (a French acronym for infrared absorption spectroscopy by tunable diode lasers) instrument has been developed for in situ measurements of several tracer and chemically active species in the stratosphere. Laser absorption takes place in an open Herriott multipass cell located under the balloon gondola, with six lead salt diode lasers as light sources. One mirror is located at the extremity of a deployable mast 3.5 m below the gondola, enabling the measurement of very low abundance species throughout a very long absorption path (up to 544 m). Three successful flights have produced concentration measurements of O3, CO, CO2, CH4, N2O, NO2, NO, HNO3, HCl, HOCl, COF2, and H2O2. Fast measurements (every 1.1 s) allow one to obtain a vertical resolution of 5 m for the profiles. A detection limit of a few tens of parts per trillion in volume has been demonstrated. Uncertainties of 3%-5% are estimated for the most abundant species rising to about 30% for the less abundant ones, mainly depending on the laser linewidth and the signal-to-noise ratio.

Abstract. The ENVISAT validation programme for the atmospheric instruments MIPAS, SCIAMACHY and GOMOS is based on a number of balloon-borne, aircraft, satellite and ground-based correlative measurements. In particular the activities of validation scientists were coordinated by ESA within the ENVISAT Stratospheric Aircraft and Balloon Campaign or ESABC. As part of a series of similar papers on other species [this issue] and in parallel to the contribution of the individual validation teams, the present paper provides a synthesis of comparisons performed between MIPAS CH 4 and N 2 O profiles produced by the current ESA operational software (Instrument Processing Facility version

Abstract. During several balloon flights inside the Arctic polar vortex in early 2003, unusual trace gas distributions were observed, which indicate a strong influence of mesospheric air in the stratosphere. The tuneable diode laser (TDL) instrument SPIRALE (Spectroscopie InFrarouge par Absorption de Lasers Embarqués) measured unusually high CO values (up to 600 ppb) on 27 January at about 30 km altitude. The cryosampler BONBON sampled air masses with very high molecular Hydrogen, extremely low SF6 and enhanced CO values on 6 March at about 25 km altitude. Finally, the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) Fourier Transform Infra-Red (FTIR) spectrometer showed NOy values which are significantly higher than NOy* (the NOy derived from a correlation between N2O and NOy under undisturbed conditions), on 21 and 22 March in a layer centred at 22 km altitude. Thus, the mesospheric air seems to have been present in a layer descending from about 30 km in late January to 25 km altitude in early March and about 22 km altitude on 20 March. We present corroborating evidence from a model study using the KASIMA (KArlsruhe Simulation model of the Middle Atmosphere) model that also shows a layer of mesospheric air, which descended into the stratosphere in November and early December 2002, before the minor warming which occurred in late December 2002 lead to a descent of upper stratospheric air, cutting of a layer in which mesospheric air is present. This layer then descended inside the vortex over the course of the winter. The same feature is found in trajectory calculations, based on a large number of trajectories started in the vicinity of the observations on 6 March. Based on the difference between the mean age derived from SF6 (which has an irreversible mesospheric loss) and from CO2 (whose mesospheric loss is much smaller and reversible) we estimate that the fraction of mesospheric air in the layer observed on 6 March, must have been somewhere between 35% and 100%.

The comparison to ACE satellite observations exhibits only a small negative bias of MIPAS which appears not to be significant. The independent satellite instruments HALOE, SAGE II, and POAM III confirm in common for the spring-summer time period a negative bias of MIPAS in the Arctic and a positive bias in the Antarctic middle and upper stratosphere exceeding frequently the combined systematic error limits. In contrast to the ESA operational processor, the IMK/IAA retrieval code allows accurate inference of NO 2 volume mixing ratios under consideration of all important non-LTE proCorrespondence to: G. Wetzel (gerald.wetzel@imk.fzk.de) cesses. Large differences between both retrieval results appear especially at higher altitudes, above about 50 to 55 km. These differences might be explained at least partly by non-LTE under polar winter conditions but not at mid-latitudes. Below this altitude region mean differences between both processors remain within 5% (during night) and up to 10% (during day) under undisturbed (September 2002) conditions and up to 40% under perturbed polar night conditions (February and March 2004). The intercomparison of ground-based NDACC observations shows no significant bias between the FTIR measurements in Kiruna (68 • N) and MIPAS in summer 2003 but larger deviations in autumn and winter. The mean deviation over the whole comparison period remains within 10%. A mean negative bias of 15% for MIPAS daytime and 8% for nighttime observations has been determined for UV-vis comparisons over Harestua (60 • N). Results of a pole-to-pole comparison of ground-based DOAS/UV-visible sunrise and MIPAS mid-morning column data has shown that the mean agreement in 2003 falls within the accuracy limit of the comparison method. Altogether, it can be indicated that MIPAS NO 2 profiles yield valuable information on the vertical distribution of NO 2 in the lower and middle stratosphere (below about 45 km) during day and night with an overall accuracy of about 10-20% and a precision of typically 5-15% such that the data are useful for scientific studies. In cases where extremely high NO 2 occurs in the mesosphere (polar winter) retrieval results in the lower and middle stratosphere are less accurate than under undisturbed atmospheric conditions.