1Institute for Marine and Atmospheric research Utrecht, Utrecht University, Utrecht, The Netherlands
2Max Planck Institute for Chemistry, Air Chemistry Division, Mainz, Germany
3Karlsruhe Institute of Technology, Institute for Meteorology and Climate Research – Atmospheric Trace Gases and Remote Sensing, Karlsruhe, Germany
Abstract. More than 450 air samples that were collected in the upper troposphere – lower stratosphere (UTLS) region around the tropopause (TP) by the CARIBIC aircraft (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) have been analyzed for molecular hydrogen (H2) mixing ratios (m(H2)) and H2 isotopic composition (deuterium content, δD).
More than 120 of the analysed samples consisted of air from the lowermost stratosphere (LMS). These show that m(H2) does not vary appreciably with O3-derived height above the thermal TP, whereas δD does increase with height. The isotope enrichment is caused by competing H2 production and destruction processes that enrich the stratospheric H2 reservoir in deuterium (D); the exact shapes of the profiles are mainly determined by mixing of stratospheric with tropospheric air. Tight negative correlations are found between δD and the mixing ratios of methane (CH4) and nitrous oxide (N2O), as a result of the relatively long lifetimes of these three species. The correlations are described by δ D [‰]=-0.35 · m(CH4)[ppb]+768 and δD [‰]=-1.90 · m(N2O)[ppb]+745. These correlations are similar to previously published results and likely hold globally.
Samples that were collected from the Indian subcontinent up to 40° N before, during and after the summer monsoon season show no significant seasonal change in m(H2), but δD is up to 15‰ lower in the July, August and September monsoon samples. This δD lowering is correlated with m(CH4) increase. The significant correlation with m(CH4) and the absence of a perceptible m(H2) increase that accompanies the δD lowering indicates that microbial production of very D-depleted H2 in the wet season may contribute to this phenomenon.
Some of the samples have very high m(H2) and very low δD values, which indicates a pollution effect. Aircraft engine exhaust plumes are a suspected cause, since the effect mostly occurs in samples collected close to airports, but no similar signals are found in other chemical tracers to support this. The isotopic source signature of the H2 pollution seems to be on the low end of the signature for fossil fuel burning.