How do Cl concentrations matter for the simulation of CH₄ and <i>δ</i>¹³C(CH₄) and estimation of the CH₄ budget through atmospheric inversions?

Abstract

Atmospheric methane (CH4) concentrations have been rising since 2007 due to an imbalance between CH4 sources and sinks. The CH4 budget is generally estimated through top-down approaches using chemistry transport models (CTMs) and CH4 observations as constraints. The atmospheric isotopic CH4 composition, δ13C(CH4), can also provide additional constraints and helps to discriminate between emission categories. Nevertheless, to be able to use the information contained in these observations, the models must correctly account for processes influencing δ13C(CH4). The oxidation by chlorine (Cl) likely contributes less than 5 % to the total oxidation of atmospheric CH4. However, the large kinetic isotope effect of the Cl sink produces a large fractionation of 13C, compared with 12C in atmospheric CH4, and thus may strongly influence δ13C(CH4). When integrating the Cl sink in their setup to constrain the CH4 budget, which is not yet standard, atmospheric inversions prescribe different Cl fields, therefore leading to discrepancies between flux estimates. To quantify the influence of the Cl concentrations on CH4, δ13C(CH4), and CH4 budget estimates, we perform sensitivity simulations using four different Cl fields. We also test removing the tropospheric and the entire Cl sink. We find that the Cl fields tested here are responsible for between 0.3 % and 8.5 % of the total chemical CH4 sink in the troposphere and between 1.0 % and 1.6 % in the stratosphere. Prescribing these different Cl amounts in atmospheric inversions can lead to differences of up to 53.8 Tg CH4 yr−1 in global CH4 emissions and of up to 4.7 ‰ in the globally averaged isotopic signature of the CH4 source δ13C(CH4)source), although these differences are much smaller if only recent Cl fields are used. More specifically, each increase by 1000 molec.cm-3 in the mean tropospheric Cl concentration would result in an adjustment by +11.7 Tg CH4 yr−1, for global CH4 emissions, and −1.0 ‰, for the globally averaged δ13C(CH4)source. Our study also shows that the CH4 seasonal cycle amplitude is modified by less than 1 %–2 %, but the δ13C(CH4) seasonal cycle amplitude can be significantly modified by up to 10 %–20 %, depending on the latitude. In an atmospheric inversion performed with isotopic constraints, this influence can result in significant differences in the posterior source mixture. For example, the contribution from wetland emissions to the total emissions can be modified by about 0.8 % to adjust the globally averaged δ13C(CH4)source, corresponding to a 15 Tg CH4 yr−1 change. This adjustment is small compared to the current wetland source uncertainty, albeit far from negligible. Finally, tested Cl concentrations have a large influence on the simulated δ13C(CH4) vertical profiles above 30 km and a very small impact on the simulated CH4 vertical profiles. Overall, our model captures the observed CH4 and δ13C(CH4) vertical profiles well, especially in the troposphere, and it is difficult to prefer one Cl field over another based uniquely on the available observations of the vertical profiles.