[1] Since 1996, quality assurance experiments of electrochemical concentration cell (ECC) ozonesondes of two different model types (SPC-6A and ENSCI-Z) have been conducted in the environmental simulation facility at the Research Centre Juelich within the framework of the Juelich Ozone Sonde Intercomparison Experiment (JOSIE). The experiments have shown that the performance characteristics of the two ECC-sonde types can be significantly different, even when operated under the same conditions. Particularly above 20 km the ENSCI-Z sonde tends to measure 5-10% more ozone than the SPC-6A sonde. Below 20 km the differences are 5% or less, but appear to show some differences with year of manufacture. There is a significant difference in the ozone readings when sondes of the same type are operated with different cathode sensing solutions. Testing the most commonly used sensing solutions showed that for each ECCmanufacturer type the use of 1.0% KI and full buffer gives 5% larger ozone values compared with the use of 0.5% KI and half buffer, and as much as 10% larger values compared with 2.0% KI and no buffer. For ozone sounding stations performing long term measurements this means that changing the sensing solution type or ECC-sonde type can easily introduce a change of ±5% or more in their records, affecting determination of ozone trends. Standardization of operating procedures for ECC-sondes yields a precision better than ±(3-5)% and an accuracy of about ±(5-10)% up to 30 km altitude.Citation: Smit, H. G. J., et al. (2007), Assessment of the performance of ECC-ozonesondes under quasi-flight conditions in the environmental simulation chamber:

Abstract. Tentative estimates, using three-dimensional chemistry and transport models, have suggested small ozone increases in the upper troposphere resulting from current aircraft emissions, but have also concluded to significant deficiencies in today's models and to the need to improve them through comparison with extended data sets. The Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft (MOZAIC) program was initiated in 1993 by European scientists, aircraft manufacturers, and airlines to collect experimental data. Its goal is to help understand the atmosphere and how it is changing under the influence of human activity, with particular interest in the effects of aircraft. MOZAIC consists of automatic and regular measurements of ozone and water vapor by five long range passenger airliners flying all over the world. The aim is not to detect direct effects of aircraft emissions on the ozone budget inside the air traffic corridors but to build a large database of measurements to allow studies of chemical and physical processes in the atmosphere, and hence to validate global chemistry transport models. MOZAIC data provide, in particular, detailed ozone and water vapor climatologies at 9-12 km where subsonic aircraft emit most of their exhaust and which is a very critical domain (e.g., radiatively and stratosphere/troposphere exchanges) still imperfectly described in existing models. This will be valuable to improve knowledge about the processes occuring in the upper troposphere and the lowermost stratosphere, and the model treatment of near tropopause chemistry and transport. During MOZAIC I (January 1993-September 1996), fully automatic devices were developed,

[1] On the basis of extensive laboratory and field tests of electrochemical concentration cell (ECC) ozonesondes, a height-dependent artifact in ozone profile measurements was found that is primarily due to side reactions of the phosphate buffers used in the ''standard'' 1% potassium iodide sensing solution. The influence of the buffers was revealed as a result of new, direct measurements of the ozonesonde pump flow rate efficiency made in an environmental chamber using an oil bubble flowmeter developed at National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory (NOAA/CMDL). The new flow rate measurements give pump efficiency correction factors that are 2 and 15% greater at 100 and 5 hPa, respectively, than those used in currently recommended procedures. Profile measurements using ozonesondes with differing ECC sensor solutions, on dual-sonde balloons and experiments in a simulation chamber, show that the impact of the buffers is most pronounced above the ozone partial pressure maximum. The effect is about a 10-15% overmeasurement of ozone at an altitude of 30 km. Careful consideration must be given to the combination of the sensing solution composition and pump efficiency correction if representative ozone profiles are to be obtained from ozonesonde measurements.

A series of measurements over the equatorial Pacific in March 1993 showed that the volume mixing ratios of ozone were frequently well below 10 nanomoles per mole both in the marine boundary layer (MBL) and between 10 kilometers and the tropopause. These latter unexpected results emphasize the enormous variability of tropical tropospheric ozone and hydroxyl concentrations, which determine the oxidizing efficiency of the troposphere. They also imply a convective short circuit of marine gaseous emissions, such as dimethyl sulfide, between the MBL and the uppermost troposphere, leading, for instance, to sulfate particle formation.

[1] A balloon flight to compare 18 ozonesondes with an ozone photometer and with ozone column measurements from Dobson and Brewer spectrophotometers was completed in April 2004. The core experiment consisted of 12 electrochemical concentration cell ozonesondes, 6 from Science Pump Corporation (SP) and 6 from ENSCI Corporation (ES), prepared with cathode solution concentrations of 0.5% KI (half buffer) and 1.0% KI (full buffer). Auxiliary ozonesondes consisted of two electrochemical concentration cell sondes with 2.0% KI (no buffer), two reconditioned sondes, and two Japanese-KC96 sondes. Precision of each group of similarly prepared ozonesondes was <2-3%. The six ozonesondes prepared according to the manufacturer's recommendations (SP, 1.0% KI, ES 0.5% KI) overestimated the photometer measurements by 5-10% in the stratosphere, but provided ozone columns in good agreement with the ground-based spectrophotometer measurements. This is consistent with the difference ($5%) in ozone photometer and column measurements observed during the experiment. Using cathode cell concentrations of 1.0% KI for ES sondes caused overestimates of the photometer by 10-15% and of ozone column by 5-10%. In contrast, 0.5% KI in SP sondes led to good agreement with the photometer, but underestimates of ozone column. The KC96 sondes underestimated the photometer measurements by about 5-15% at air pressures above 30 hPa. Agreement was within 5% at lower pressures. Diluting the solution concentration and the buffers from 1.0% to 0.5% KI causes an approximately linear pressure-dependent decrease in ozone for both SP and ES sondes, ratio (0.5 KI/1.0 KI) = 0.9 + 0.024 * log 10 (Pressure).