A detailed model is presented of methane photochemistry in the primitive terrestrial atmosphere along with speculation about its interpretation. Steady-state CH4 mixing ratios of 10−6−10−4 could have been maintained by a methane source of about 1011 cm−2 s−1, which is comparable to the modern biogenic methane production rate. In the absence of a source, methane would have disappeared in < 104 years, being either oxidized, or polymerized into more complex hydrocarbons. The source strength needed to maintain a steady CH4 mixing ratio and the degree to which methane could have polymerized to form higher hydrocarbons depend upon the amount of CO2 present in the early atmosphere. The dependence on H2 is much weaker. Infrared absorption by methane, and especially by other hydrocarbon species, may have supplemented the greenhouse warming due to carbon dioxide. A radiative model is needed to establish this effect quantitatively. The destruction of the methane greenhouse early in the Proterozoic may have triggered the Huronian glaciation. These calculations also suggest that atmospheres rich in both CO2 and CH4 may be photochemically unstable with respect to conversion to CO.
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