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Ozone is generally assumed to have weak diurnal variations in the free troposphere due to lower production rates than in the boundary layer, in addition to a much lower NO titration and the absence of dry deposition at the surface. However, this hypothesis has not been proven due to a lack of high frequency observations at multiple times per day. For the first time, we take benefit from the frequent O3 vertical profiles measured above Frankfurt in the framework of the MOZAIC-IAGOS program to investigate the diurnal variations of O3 mixing ratios at multiple pressure levels throughout the troposphere. With about 21,000 aircraft profiles between 1994 and 2012 (98 per month on average), distributed throughout the day, this is the only dataset that can allow such a study. As expected, strong diurnal variations are observed close to the surface, in particular during spring and summer (enhanced photochemistry and surface deposition). Higher in altitude, our observations show a decrease of the diurnal cycle, with no diurnal cycle discernible above 750 hPa, whatever the season. Similar results are observed for the different percentiles of the O3 distribution (5th, 25th, 50th, 75th, 95th). An insight of the changes of the diurnal cycles between 1994–2003 and 2004–2012 is also given. We found higher O3 mixing ratios during the latter period, particularly on the lowest pressure levels, despite lower mixing ratios during summer.

Diurnal cycle of ozone throughout the troposphere over Frankfurt as measured by MOZAIC-IAGOS commercial aircraft