Electrochemical concentration cell (ECC) ozonesonde pump efficiency measurements and tests on the sensitivity to ozone of buffered and unbuffered ECC sensor cathode solutions

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.