Metastable methane clathrate particles as a source of methane to the martian atmosphere

The observations of methane made by the PFS instrument onboard Mars Express exhibit a definite correlation between methane mixing ratio, water vapor mixing ratio, and cloud optical depth. The recent data obtained from ground-based telescopes seem to confirm the correlation between methane and water vapor. In order to explain this correlation, we suggest that the source of gaseous methane is atmospheric, rather than at the solid surface of the planet, and that this source may consist of metastable submicronic particles of methane clathrate hydrate continuously released to the atmosphere from one or several clathrate layers at depth, according to the phenomenon of “anomalous preservation” evidenced in the laboratory. These particles, lifted up to middle atmospheric levels due to their small size, and therefore filling the whole atmosphere, serve as condensation nuclei for water vapor. The observed correlation between methane and water vapor mixing ratios could be the signature of the decomposition of the clathrate crystals by condensation-sublimation processes related to cloud activity. Under the effect of water condensation on crystal walls, metastability could be broken and particles be eroded, resulting in a subsequent irreversible release of methane to the gas phase. Using PFS data, and according to our hypothesis, the lifetime of gaseous methane is estimated to be smaller than an upper limit of 6 ± 3 months, much smaller than the lifetime of 300 yr calculated from atmospheric chemical models. The reason why methane has a short lifetime might be the occurrence of heterogeneous chemical decomposition of methane in the subsurface, where it is known since Viking biology experiments that oxidants efficiently decompose organic matter. If true, it is shown by using existing models of H₂O₂ penetration in the regolith that methane could prevent H₂O₂ from penetrating in the subsurface, and further oxidizing the soil, at depths larger than a few millimeters. The present source of methane clathrate, acting over the last few hundred thousand or million years, could have given rise to the thin CO₂-ice layer covering the permanent water ice south polar cap. The hypothesis proposed in this paper requires, to be validated, a number of laboratory experiments studying the stability of methane clathrates in martian atmospheric conditions, and the kinetics and amplitude of clathrate particle erosion in presence of condensing water vapor. Detailed future observations of methane, and associated modeling, will allow to more accurately quantify the production rate of methane clathrate, its temporal variability at seasonal scale, and possibly to locate the source(s) of clathrates at the surface.