There's a nice story by Richard Lovett in Wednesday's San Diego Union-Tribune on the sort of chemistry that could be going on in the martian crust, as currently being studied in the depths of the Atlantic. It doesn't mention the martian methane specifically, but these reactions between olivine (a major component of the peridotites on the floor of the Atlantic) and water are exactly the sort of serpentinization reactions that might be in play on Mars. As either an alternative to life (in the methane generating stakes) or as a fuel source for life, serpentinization looks really interesting. The difficulty in my mind is how you get chunks of rock from the martian mantle up to the crust where the water can get at them -- the martian crust is reckoned to be a pretty thick thing. However, the fact that I don't know how it happens doesn't mean that it doesn't; after all, some olivine has been identified at the surface by TES, and "what has happened can happen." (The latest results on this from Themis are in this pdf abstract). Whether the mechanisms that got olivine to the surface in the past are getting it into contact with water today is obviously another question.
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