28Hydrogen gas, H2, is generated in alkaline hydrothermal vents from reactions of iron 29 containing minerals with water during a geological process called serpentinization. It has been 30 a source of electrons and energy since there was liquid water on the early Earth, and it fuelled 31 early anaerobic ecosystems in the Earth's crust 1-3 . H2 is the electron donor for the most 32 ancient route of biological CO2 fixation, the acetyl-CoA (or Wood-Ljungdahl) pathway, 33 which unlike any other autotrophic pathway simultaneously supplies three key requirements 34 for life: reduced carbon in the form of acetyl groups, electrons in the form of reduced 35 ferredoxin, and ion gradients for energy conservation in the form of ATP 4,5 . The pathway is 36 linear, not cyclic, it releases energy rather than requiring energy input, its enzymes are replete 37 with primordial metal cofactors 6,7 , it traces to the last universal common ancestor 8 and abiotic, 38 geochemical organic syntheses resembling segments of the pathway occur in hydrothermal 39 vents today 9,10 . Laboratory simulations of the acetyl-CoA pathway's reactions include the 40 nonenzymatic synthesis of thioesters from CO and methylsulfide 11 , the synthesis of acetate 12 41 and pyruvate 13 from CO2 using native iron or external electrochemical potentials 14 as the 42 electron source. However, a full abiotic analogue of the acetyl-CoA pathway from H2 and 43 CO2 as it occurs in life has not been reported to date. Here we show that three hydrothermal 44 mineralsawaruite (Ni3Fe), magnetite (Fe3O4) and greigite (Fe3S4)catalyse the fixation 45 of CO2 with H2 at 100 °C under alkaline aqueous conditions. The product spectrum includes 46 formate (100 mM), acetate (100 µM), pyruvate (10 µM), methanol (100 µM), and methane. 47 With these simple catalysts, the overall exergonic reaction of the acetyl-CoA pathway is 48 facile, shedding light on both the geochemical origin of microbial metabolism and on the 49 nature of abiotic formate and methane synthesis in modern hydrothermal vents. 50 51 Organic synthesis in hydrothermal vents is relevant to life's origin because the reactions 52 involve sustained energy release founded in the disequilibrium between CO2 and the vast 53 amounts of molecular hydrogen, H2, generated in the Earth's crust during 54 serpentinization 1,2,9,10,[15][16][17][18][19] . Enzymatic versions of those abiotic reactions occur in core energy 55 metabolism in acetogens and methanogens 4-7 , ancient anaerobic autotrophs that live from H2 56 and CO2 via the acetyl-CoA pathway and that still inhabit the crust today 7 . Though the 57 enzymes that catalyse the microbial reactions are well investigated 4-7 , the catalysts promoting 58 the abiotic reactions in vents today, and that might have been instrumental at life's origin, are 59 not fully understood 9 . To probe the mechanisms of hydrothermal metabolic reactions 60 3 emulating ancient pathways, we investigated three iron minerals that naturally occur in 61 hydrothermal vents: greigite (...