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Abstract:
An issue of O-3-driven artefact production of O-3 in the upper troposphere/lowermost stratosphere (UT/LMS) air analysed in the CARIBIC-1 project is being discussed. By confronting the CO mixing and isotope ratios obtained from different analytical instrumentation, we (i) reject natural/artificial sampling and mixing effects as possible culprits of the problem, (ii) ascertain the chemical nature and quantify the strength of the contamination, and (iii) demonstrate successful application of the isotope mass-balance calculations for inferring the isotope composition of the contamination source. The delta O-18 values of the latter indicate that the oxygen is very likely being inherited from O-3. The delta C-13 values hint at reactions of trace amounts of organics with stratospheric O3 that could have yielded the artificial CO. While the exact contamination mechanism is not known, it is clear that the issue pertains only to the earlier (first) phase of the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) project. Finally, estimated UT/LMS ozone delta O-18 values are lower than those observed in the stratosphere within the same temperature range, suggesting that higher pressures (240-270 hPa) imply lower isotope fractionation controlling the local delta O-18(O-3) value.
