Ioannis Panagiotou, Tim Lichtenberg, Shang-Min Tsai, Harrison Nicholls

Volatile outgassing from planetary interiors controls the composition of rocky exoplanets' secondary atmospheres. However, observations indicate that disequilibrium processes, such as photochemistry and vertical transport, can strongly alter the chemical structure of Hot Jupiters. Which process dominates under different types of rocky planets, and how outgassing and photochemistry jointly determine the atmospheric composition, remain open questions. Sulfur species are promising tracers of interior-atmosphere coupling because their atmospheric abundances are sensitive to both mantle redox state and stellar irradiation. The PROTEUS planetary interior-atmosphere evolution modelling framework is coupled to two chemical models, FastChem and VULCAN, for post-processed chemistry calculations. We run a grid of planetary evolution simulations spanning diverse mantle redox states, instellation fluxes, and Solar versus M-star host-star spectra. For each case, we compare atmospheric compositions under thermochemical equilibrium, only vertical transport, and vertical transport plus photochemistry. The bulk atmospheric composition remains controlled by the redox state of the mantle and outgassing history, even when disequilibrium chemistry is included. Reduced mantles produce atmospheres rich in H2, and oxidised mantles are dominated by CO2. Photochemistry affects the upper atmosphere, strongly depleting neutral volatiles and enhancing radicals, especially for highly irradiated cases. SO2 is strongly enhanced at intermediate-to-oxidised redox states. Synthetic emission spectra show that photochemical SO2 can generate absorption features at 4 um and at 7.3 / 8.7 um, reaching ~60 ppm and ~100 ppm, before sequentially returning to the outgassed signatures of ~30 ppm and ~50 ppm for the oxidised mantle redox state. These signatures are detectable with JWST, motivating targeted observational campaigns.