Development of nascent autotrophic carbon fixation systems in various redox conditions of the fluid degassing in early Earth
<p><strong>Abstract.</strong> Strategies for the origin and development of primary metabolism on early Earth were determined by the two main regimes of degassing of Earth in the form of CO<sub>2</sub> or CH<sub>4</sub> fluid impulses. Among the existing theories of the autotrophic origin of the life, CO<sub>2</sub> is usually considered the carbon source for nascent autotrophic metabolism. However, the ancestral carbon used in metabolism may have been derived from CH<sub>4</sub> if the outflow of magma fluid to the surface of the Earth consisted mainly of methane. Primary biochemical systems are present in methane degassing regimes developed in an environment of high partial pressure of methane, which is a source of carbon for nascent metabolic systems. Due to the absence of molecular oxygen in the Archaean conditions, this metabolism would have been anaerobic, i.e., oxidation of methane must be realized by inorganic high-potential electron acceptors. In light of the primacy and predominance of CH<sub>4</sub>-dependent metabolism in hydrothermal systems of the ancient Earth, we propose a model of carbon fixation, which is a sequence of reactions in a hypothetical methane-fumarate (MF) cycle. Thermodynamics calculations showed a high efficiency of oxidation of methane to acetate (methanotrophic acetogenesis) by oxidized nitrogen compounds in hydrothermal systems. Thermodynamically favorable were also reactions involving the introduction of carbon methane into the intermediates of the proposed MF cycle. The methane oxidation reactions with the use of oxygen of iron mineral buffers are closer to the equilibrium state, which apparently determines the possibilities of primordial cycle flow in the forward or reverse directions.</p>