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Abstract Understanding the surface temperature and interior structure of cold-to-temperate sub-Neptunes is critical for assessing their habitability, yet direct observations are challenging. In this study, we investigate the impact of water condensation on the atmospheric compositions of sub-Neptunes, focusing on the implications for James Webb Space Telescope (JWST) spectroscopic observations. By modeling the atmospheric photochemistry of two canonical sub-Neptunes, K2-18 b and LHS 1140 b, both with and without water condensation and with and without thick atmospheres, we demonstrate that water condensation can significantly affect the predicted atmospheric compositions. This effect is driven by oxygen depletion from the condensation of water vapor and primarily manifests as an increase in the C/O ratio within the photochemically active regions of the atmosphere. This change in composition particularly affects planets with thin H₂-dominated atmospheres, leading to a transition in dominant nitrogen and carbon carriers from N₂and oxygen-rich species like CO/CO₂toward heavier hydrocarbons and nitriles. While our models do not fully account for the loss mechanisms of these higher-order species, such molecules can go on to form more refractory molecules or hazes. Planets with thin H₂-rich atmospheres undergoing significant water condensation are thus likely to exhibit very hazy atmospheres. The relatively flat JWST spectra observed for LHS 1140 b could be consistent with such a scenario, suggesting a shallow surface with extensive water condensation or a high atmospheric C/O ratio. Conversely, the JWST observations of K2-18 b are better aligned with a volatile-rich mini-Neptune with a thick atmosphere. 

Abstract Temperate exoplanets between the sizes of Earth and Neptune, known as “sub-Neptunes,” have emerged as intriguing targets for astrobiology. It is unknown whether these planets resemble Earth-like terrestrial worlds with a habitable surface, Neptune-like giant planets with deep atmospheres and no habitable surface, or something exotic in between. Recent JWST transmission spectroscopy observations of the canonical sub-Neptune, K2-18 b, revealed ~1% CH₄, ~1% CO₂, and a nondetection of CO in the atmosphere. While previous studies proposed that the observed atmospheric composition could help constrain the lower atmosphere's conditions and determine the interior structure of sub-Neptunes like K2-18 b, the possible interactions between the atmosphere and a hot, supercritical water ocean at its base remain unexplored. In this work, we investigate whether a global supercritical water ocean, resembling a planetary-scale hydrothermal system, can explain these observations on K2-18 b–like sub-Neptunes through equilibrium aqueous geochemical calculations. We find that the observed atmospheric CH₄/CO₂ratio implies a minimum ocean temperature of ~710 K, whereas the corresponding CO/CO₂ratio allows ocean temperatures up to ~1070 K. These results indicate that a global supercritical water ocean on K2-18 b is plausible. While life cannot survive in such an ocean, this work represents the first step toward understanding how a global supercritical water ocean may influence observable atmospheric characteristics on volatile-rich sub-Neptunes. Future observations with better-constrained CO and NH₃mixing ratios could further help distinguish between possible interior compositions of K2-18 b.