Viability of pyrite pulled metabolism in the ‘iron-sulfur world’ theory: Quantum chemical assessment

The viability of pyrite-pulled metabolism in the ‘iron-sulfur world’ theory was assessed using a simple model of iron–nickel sulfide (Fe–Ni–S) surface and data obtained from quantum chemical calculations. We have investigated how the individual reactions in the carbon fixation cycle (carboxylic acids formation) on an Fe–Ni–S surface could have operated to produce carboxylic acids from carbon oxide and water. The proposed model cycle reveals how the individual reactions might have functioned and provides the thermodynamics of each step of the proposed pathway. The feasibility of individual reactions, as well the whole cycle was considered. The reaction of acetic acid production from CH3SH and CO on an Fe–Ni sulfide surface was revealed to be endergonic with a few partial steps having positive Gibbs free energy. On the other hand, the pyrite formation was found to be slightly exergonic. The significance of the catalytic activity of transition metal sulfides in generation of acetic acid was shown. The Gibbs free energy values indicate that the acetic acid synthesis is unfavorable to proceed on the studied Fe–Ni–S model under simulated conditions. The importance of these results in terms of a primordial chemistry on iron–nickel sulfide surfaces is discussed.