Thermodynamic constraints on the citric acid cycle and related reactions in ocean world interiors

Abstract

Icy ocean worlds attract significant interest for their astrobiological potential due to subsurface oceans, organics, and chemical energy sources. We quantify thermodynamic viability of metabolism-relevant reactions at pressure-temperature conditions of Enceladus, Europa, Titan, Ganymede, and the Lost City Hydrothermal Field for comparison. We examine the tricarboxylic acid (TCA) cycle and a plausible prebiotic reaction network leading to it, using DEWPython (based on the Deep Earth Water model) and SUPCRT to compute equilibrium constants and Gibbs free energy changes across temperatures from 0-1200{\deg}C and pressures between 1 bar-60 kbar. We found that across most oceanic P-T profiles, certain TCA cycle species accumulate (citrate, succinate) while others diminish (fumarate, oxaloacetate), suggesting ocean worlds' conditions may not thermodynamically favor a unidirectional TCA cycle, requiring additional energy to overcome bottlenecks. Similar bottlenecks exist at Lost City, which is inhabited. In the prebiotic network, pyruvate and acetate show remarkable stability, feeding the TCA cycle through citrate production, bypassing the oxaloacetate bottleneck. Formation of most TCA cycle species from inorganic compounds (CO$_2$ + H$_2$) is highly favored throughout ocean world geotherms, except for oxaloacetate. While based on uncertain chemical concentrations, our non-equilibrium thermodynamic predictions are relatively insensitive to activity changes and may aid interpretation of future mission data. [ABRIDGED]