H. Küllmann

Validation of the Aura Microwave Limb Sounder ClO measurements

We assess the quality of the version 2.2 (v2.2) ClO measurements from the Microwave Limb Sounder (MLS) on the Earth Observing System Aura satellite. The MLS v2.2 ClO data are scientifically useful over the range 100 to 1 hPa, with a single- profile precision of similar to 0.1 ppbv throughout most of the vertical domain. Vertical resolution is similar to 3-4 km. Comparisons with climatology and correlative measurements from a variety of different platforms indicate that both the amplitude and the altitude of the peak in the ClO profile in the upper stratosphere are well determined by MLS. The latitudinal and seasonal variations in the ClO distribution in the lower stratosphere are also well determined, but a substantial negative bias is present in both daytime and nighttime mixing ratios at retrieval levels below (i. e., pressures larger than) 22 hPa. Outside of the winter polar vortices, this negative bias can be eliminated by subtracting gridded or zonal mean nighttime values from the individual daytime measurements. In studies for which knowledge of lower stratospheric ClO mixing ratios inside the winter polar vortices to better than a few tenths of a ppbv is needed, however, day - night differences are not recommended and the negative bias must be corrected for by subtracting the estimated value of the bias from the individual measurements at each affected retrieval level.

Chemical depletion of Arctic ozone in winter 1999/2000

During Arctic winters with a cold, stable stratospheric circulation, reactions on the surface of polar stratospheric clouds (PSCs) lead to elevated abundances of chlorine monoxide (ClO) that, in the presence of sunlight, destroy ozone. Here we show that PSCs were more widespread during the 1999/2000 Arctic winter than for any other Arctic winter in the past two decades. We have used three fundamentally different approaches to derive the degree of chemical ozone loss from ozonesonde, balloon, aircraft, and satellite instruments. We show that the ozone losses derived from these different instruments and approaches agree very well, resulting in a high level of confidence in the results. Chemical processes led to a 70% reduction of ozone for a region ∼1 km thick of the lower stratosphere, the largest degree of local loss ever reported for the Arctic. The Match analysis of ozonesonde data shows that the accumulated chemical loss of ozone inside the Arctic vortex totaled 117 ± 14 Dobson units (DU) by the end of winter. This loss, combined with dynamical redistribution of air parcels, resulted in a 88 ± 13 DU reduction in total column ozone compared to the amount that would have been present in the absence of any chemical loss. The chemical loss of ozone throughout the winter was nearly balanced by dynamical resupply of ozone to the vortex, resulting in a relatively constant value of total ozone of 340 ± 50 DU between early January and late March. This observation of nearly constant total ozone in the Arctic vortex is in contrast to the increase of total column ozone between January and March that is observed during most years.

Intercomparison of ozone profile measurements from ASUR, SCIAMACHY, MIPAS, OSIRIS, and SMR

The airborne submillimeter radiometer ( ASUR) was deployed onboard the Falcon research aircraft during the scanning imaging absorption spectrometer for atmospheric cartography ( SCIAMACHY) validation and utilization experiment ( SCIAVALUE) and the European polar stratospheric cloud and lee wave experiment ( EuPLEx) campaigns. A large number of ozone profile measurements were performed over a latitude band spanning from 5 degrees S to 80 degrees N in September 2002 and February/March 2003 during the SCIAVALUE and around the northern polar latitudes in January/February 2003 during the EuPLEx. Both missions amassed an ample microwave ozone profile data set that is used to make quantitative comparisons with satellite measurements in order to assess the quality of the satellite retrievals. In this paper, the ASUR ozone profile measurements are compared with measurements from SCIAMACHY and Michelson interferometer for passive atmospheric sounding ( MIPAS) on Environmental Satellite and optical spectrograph and infrared imager system ( OSIRIS) and submillimeter radiometer ( SMR) on the Odin satellite. The cross comparisons with the criterion that the ASUR measurements are performed within +/- 1000 km and +/- 6 hrs of the satellite observations show a good agreement with all the four satellite sensors. The differences in data values are the following: -4 to +8% for ASUR-SCIAMACHY ( operational product, v2.1), within +/- 15% for ASUR-SCIAMACHY ( scientific product, v1.62), up to +6% for ASUR-MIPAS ( operational product v4.61) and ASUR- MIPAS ( scientific product v1-O(3)-1), up to 17% for ASUR- OSIRIS ( v012), and -6 to 17% for ASUR- SMR ( v222) between the 20- and 40- km altitude range depending on latitude. Thus, the intercomparisons provide important quantitative information about the quality of the satellite ozone profiles, which has to be considered when using the data for scientific analyses.

Arctic ozone depletion in 2002–2003 measured by ASUR and comparison with POAM observations

We present ozone loss estimated from airborne measurements taken during January-February and March in the Arctic winter 2002/2003. The first half of the winter was characterized by unusually cold temperatures and the second half by a major stratospheric sudden warming around 15-18 January 2003. The potential vorticity maps show a vortex split in the lower stratosphere during the major warming (MW) in late January and during the minor warming in mid-February due to wave 1 amplification. However, the warming can be termed as a vortex displacement event as there was no vortex split during the MW period at 10 hPa. Very low temperatures, large areas of polar stratospheric clouds (PSCs), and high chlorine activation triggered significant ozone loss in the early winter, as the vortex moved to the midlatitude regions. The ozone depletion derived from the ASUR measurements sampled inside the vortex, in conjunction with the Mimosa-Chim model tracer, shows a maximum of 1.3 +/- 0.2 ppmv at 450-500 K by late March. The partial column loss derived from the ASUR ozone profiles reaches up to 61 +/- 4 DU in 400-550 K in the same period. The evolution of ozone and ozone loss assessed from the ASUR measurements is in very good agreement with POAM observations. The reduction in ozone estimated from the POAM measurements shows a similar maximum of 1.3 +/- 0.2 ppmv at 400-500 K or 63 +/- 4 DU in 400-550 K in late March. Our study reveals that the Arctic winter 2002/2003 was unique as it had three minor warmings and a MW, yet showed large loss in ozone. No such feature was observed in any other Arctic winter in the 1989-2010 period. In addition, an unusually large ozone loss in December, around 0.5 +/- 0.2 ppmv at 450-500 K or 12 +/- 1 DU in 400-550 K, was estimated for the first time in the Arctic. A careful and detailed diagnosis with all available published results for this winter exhibits an average ozone loss of 1.5 +/- 0.3 ppmv at 450-500 K or 65 +/- 5 DU in 400-550 K by the end of March, which exactly matches the ozone depletion derived from the ASUR, POAM and model data. The early ozone loss together with considerable loss afterwards put the warm Arctic winter 2002/2003 amongst the moderately cold winters in terms of the significance of the ozone loss.

Trajectory studies of large HNO3‐containing PSC particles in the Arctic: Evidence for the role of NAT

Large (5 to >20 μm diameter) nitric-acid-containing polar stratospheric cloud (PSC) particles were observed in the Arctic stratosphere during the winter of 1999–2000. We use a particle growth and sedimentation model to investigate the environment in which these particles grew and the likely phase of the largest particles. Particle trajectory calculations show that, while simulated nitric acid dihydrate (NAD) particle sizes are significantly smaller than the observed maximum particle sizes, nitric acid trihydrate (NAT) particle trajectories are consistent with the largest observed particle sizes.

Constraints for the photolysis rate and the equilibrium constant of ClO‐dimer from airborne and balloon‐borne measurements of chlorine compounds

We analyze measurements of ClO across the terminator taken by the Airborne Submillimeter Radiometer (ASUR) in the activated vortices of the Arctic winters of 1995/1996, 1996/1997, and 1999/2000 to evaluate the plausibility of various determinations of the ClO-dimer photolysis cross section and the rate constant controlling the thermal equilibrium between ClO-dimer and ClO. We use measured ClO during sunlit conditions to estimate total active chlorine (ClOx). As the measurements suggest nearly full chlorine activation in winter 1999/2000, we compare ClOx estimates based on various photolysis frequencies of ClO-dimer with total available inorganic chlorine (Cly), estimated from an N2O-Cly correlation established by a balloon-borne MkIV interferometer measurement. Only ClO-dimer cross sections leading to the fastest photolysis frequencies in the literature (including the latest evaluation by the Jet Propulsion Laboratory) give ClOx mixing ratios that overlap with the estimated range of available Cly. Slower photolysis rates lead to ClOx values that are higher than available Cly. We use the ClOx calculated from sunlit ClO measurements to estimate ClO in darkness based on different equilibrium constants, and compare it with ASUR ClO measurements before sunrise at high solar zenith angles. Calculations with equilibrium constants published in recent evaluations of the Jet Propulsion Laboratory give good agreement with observed ClO mixing ratios. Equilibrium constants leading to a higher ClO/ClOx ratio in darkness yield ClO values that tend to exceed observed abundances. Perturbing the rates for the ClO + BrO reaction in a manner that increases OClO formation and decreases BrCl formation leads to lower ClO values calculated for twilight conditions after sunset, resulting in better agreement with ASUR measurements.

Stratospheric trace gas measurements by the Airborne Submillimeter Radiometer ASUR during SCIA-VALUE 2002 (validation and utilisation of ENVISAT and SCIAMACHY data products)

Numerous measurements of the stratospheric trace gases ozone, HCl, HNO/sub 3/, and N/sub 2/O were performed by the Airborne Submillimeter Radiometer ASUR in September 2002. ASUR was deployed on board the German research aircraft FALCON during the SCIA-VALUE 2002 campaign. A latitudinal range between 80/spl deg/N and 5/spl deg/S was covered, enabling ASUR to perform extensive measurements in the tropics for the first time. First retrievals of stratospheric trace gas profiles are presented and their dependence on latitude is studied.