Articles | Volume 18, issue 13
Atmos. Chem. Phys., 18, 9955–9973, 2018

Special issue: The Modular Earth Submodel System (MESSy) (ACP/GMD inter-journal...

Atmos. Chem. Phys., 18, 9955–9973, 2018

Research article 13 Jul 2018

Research article | 13 Jul 2018

Investigating the yield of H2O and H2 from methane oxidation in the stratosphere

Franziska Frank1, Patrick Jöckel1, Sergey Gromov2,3, and Martin Dameris1 Franziska Frank et al.
  • 1Deutsches Zentrum für Luft- und Raumfahrt (DLR), Institut für Physik der Atmosphäre, Oberpfaffenhofen, Germany
  • 2Max-Planck-Institute for Chemistry, Air Chemistry Department, Mainz, Germany
  • 3Institute of Global Climate and Ecology Roshydromet & RAS (IGCE), Moscow, Russia

Abstract. An important driver of climate change is stratospheric water vapor (SWV), which in turn is influenced by the oxidation of atmospheric methane (CH4). In order to parameterize the production of water vapor (H2O) from CH4 oxidation, it is often assumed that the oxidation of one CH4 molecule yields exactly two molecules of H2O. However, this assumption is based on an early study, which also gives evidence that this is not true at all altitudes.

In the current study, we re-evaluate this assumption with a comprehensive systematic analysis using a state-of-the-art chemistry–climate model (CCM), namely the ECHAM/MESSy Atmospheric Chemistry (EMAC) model, and present three approaches to investigate the yield of H2O and hydrogen gas (H2) from CH4 oxidation. We thereby make use of the Module Efficiently Calculating the Chemistry of the Atmosphere (MECCA) in a box model and global model configuration. Furthermore, we use the kinetic chemistry tagging technique (MECCA-TAG) to investigate the chemical pathways between CH4, H2O and H2, by being able to distinguish hydrogen atoms produced by CH4 from H2 from other sources.

We apply three approaches, which all agree that assuming a yield of 2 overestimates the production of H2O in the lower stratosphere (calculated as 1.5–1.7). Additionally, transport and subsequent photochemical processing of longer-lived intermediates (mostly H2) raise the local yield values in the upper stratosphere and lower mesosphere above 2 (maximum  >  2.2). In the middle and upper mesosphere, the influence of loss and recycling of H2O increases, making it a crucial factor in the parameterization of the yield of H2O from CH4 oxidation. An additional sensitivity study with the Chemistry As A Boxmodel Application (CAABA) shows a dependence of the yield on the hydroxyl radical (OH) abundance. No significant temperature dependence is found. We focus representatively on the tropical zone between 23° S and 23° N. It is found in the global approach that presented results are mostly valid for midlatitudes as well. During the polar night, the method is not applicable.

Our conclusions question the use of a constant yield of H2O from CH4 oxidation in climate modeling and encourage to apply comprehensive parameterizations that follow the vertical profiles of the H2O yield derived here and take the chemical H2O loss into account.

Short summary
It is frequently assumed that one methane molecule produces two water molecules. Applying various modeling concepts, we find that the yield of water from methane is vertically not constantly 2. In the upper stratosphere and lower mesosphere, transport of intermediate H2 molecules even led to a yield greater than 2. We conclude that for a realistic chemical source of stratospheric water vapor, one must also take other sources (H2), intermediates and the chemical removal of water into account.
Final-revised paper