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Assessing the prevalence of atmospheres on rocky planets around M-dwarf stars is a top priority of exoplanet science. High-energy activity from M-dwarfs can destroy the atmospheres of these planets, which could explain the lack of atmosphere detections to date. Volcanic outgassing has been proposed as a mechanism to replenish the atmospheres of tidally-heated rocky planets. L 98-59 b, a sub-Earth transiting a nearby M dwarf, was recently identified as the most promising exoplanet to detect a volcanic atmosphere. We present the transmission spectrum of L 98-59 b from four transits observed with JWST NIRSpec G395H. Although the airless model provides an adequate fit to the data based on its $\chi^2$, an SO$_2$ atmosphere is preferred by 3.6$\sigma$ over a flat line in terms of the Bayesian evidence. Such an atmosphere would likely be in a steady state where volcanism balances escape. If so, L 98-59 b must experience at least eight times as much volcanism and tidal heating per unit mass as Io. If volcanism is driven by runaway melting of the mantle, we predict the existence of a subsurface magma ocean in L 98-59 b extending up to $R_p\sim 60-90\%$. An SO$_2$-rich volcanic atmosphere on L 98-59 b would be indicative of an oxidized mantle with an oxygen fugacity of $f\rm{O}_2>IW+2.7$, and it would imply that L 98-59 b must have retained some of its volatile endowment despite its proximity to its star. Our findings suggest that volcanism may revive secondary atmospheres on tidally heated rocky planets around M-dwarfs., Comment: Accepted for publication in ApJL, 22 pages, 13 figures

The recent inference of sulphur dioxide (SO$_2$) in the atmosphere of the hot ($\sim$1100 K), Saturn-mass exoplanet WASP-39b from near-infrared JWST observations suggests that photochemistry is a key process in high temperature exoplanet atmospheres. This is due to the low ($<$1 ppb) abundance of SO$_2$ under thermochemical equilibrium, compared to that produced from the photochemistry of H$_2$O and H$_2$S (1-10 ppm). However, the SO$_2$ inference was made from a single, small molecular feature in the transmission spectrum of WASP-39b at 4.05 $\mu$m, and therefore the detection of other SO$_2$ absorption bands at different wavelengths is needed to better constrain the SO$_2$ abundance. Here we report the detection of SO$_2$ spectral features at 7.7 and 8.5 $\mu$m in the 5-12 $\mu$m transmission spectrum of WASP-39b measured by the JWST Mid-Infrared Instrument (MIRI) Low Resolution Spectrometer (LRS). Our observations suggest an abundance of SO$_2$ of 0.5-25 ppm (1$\sigma$ range), consistent with previous findings. In addition to SO$_2$, we find broad water vapour absorption features, as well as an unexplained decrease in the transit depth at wavelengths longer than 10 $\mu$m. Fitting the spectrum with a grid of atmospheric forward models, we derive an atmospheric heavy element content (metallicity) for WASP-39b of $\sim$7.1-8.0 $\times$ solar and demonstrate that photochemistry shapes the spectra of WASP-39b across a broad wavelength range., Comment: Published in Nature

Understanding the planetary envelope composition of sub-Neptune-type exoplanets is challenging due to the inherent degeneracy in their interior composition scenarios. Particularly, the planetary envelope's H2O/H2 ratio, which can also be expressed as the O/H ratio, provides crucial insights into its original location relative to the ice line during planetary formation. Using self-consistent radiative transfer modeling and a rate-based automatic chemical network generator combined with 1D photochemical kinetic-transport atmospheric modeling, we investigate various atmospheric scenarios of temperate sub-Neptunes, ranging from H2-dominated to H2O-dominated atmospheres with equilibrium temperatures (Teq) of 250-400 K. This study includes examples such as K2-18 b (Teq = 255 K), LP 791-18 c (Teq = 324 K), and TOI-270 d (Teq = 354 K). Our models indicate that the atmospheric CO2/CH4 ratio can be used to infer the deep-interior H2O/H2 ratio. Applying this method to recent JWST observations, our findings suggest K2-18 b likely has an interior that is 50% highly enriched in water, exceeding the water content in a 100xZ scenario and suggesting a planetary formation mechanism involving substantial accretion of ices. In contrast, our model suggests that approximately 25% of TOI-270 d's interior is composed of H2O, which aligns with the conventional metallicity framework with a metallicity higher than 100xZ. Furthermore, our models identify carbonyl sulfide (OCS) and sulfur dioxide (SO2) as strong indicators for temperate sub-Neptunes with at least 10% of their interior composed of water. These results provide a method to delineate the internal composition and formation mechanisms of temperate sub-Neptunes (Teq < ~500 K) via atmospheric characterization through transmission spectroscopy., Comment: 12 pages, 5 figures, accepted to be published in ApJL

LHS 1140 b is a small planet orbiting in the habitable zone of its M4.5V dwarf host. Recent mass and radius constraints have indicated that it has either a thick H$_2$-rich atmosphere or substantial water by mass. Here we present a transmission spectrum of LHS 1140 b between 1.7 and 5.2 $\mu$m, obtained using the NIRSpec instrument on JWST. By combining spectral retrievals and self-consistent atmospheric models, we show that the transmission spectrum is inconsistent with H$_2$-rich atmospheres with varied size and metallicity, leaving a water world as the remaining scenario to explain the planet's low density. Specifically, a H$_2$-rich atmosphere would result in prominent spectral features of CH$_4$ or CO$_2$ on this planet, but they are not seen in the transmission spectrum. Instead, the data favors a high-mean-molecular-weight atmosphere (possibly N$_2$-dominated with H$_2$O and CO$_2$) with a modest confidence. Forming the planet by accreting C- and N-bearing ices could naturally give rise to a CO$_2$- or N$_2$-dominated atmosphere, and if the planet evolves to or has the climate-stabilizing mechanism to maintain a moderate-size CO$_2$/N$_2$-dominated atmosphere, the planet could have liquid-water oceans. Our models suggest CO$_2$ absorption features with an expected signal of 20 ppm at 4.2 $\mu$m. As the existence of an atmosphere on TRAPPIST-1 planets is uncertain, LHS 1140 b may well present the best current opportunity to detect and characterize a habitable world., Comment: 20 pages, 10 figures, 9 tables, accepted for publication in ApJL

Even though sub-Neptunes likely represent the most common outcome of planet formation, their natures remain poorly understood. In particular, planets near 1.5-2.5$\,R_\oplus$ often have bulk densities that can be explained equally well with widely different compositions and interior structures, resulting in grossly divergent implications for their formation. Here, we present the full 0.6-5.2$\,\mu \mathrm{m}$ JWST NIRISS/SOSS+NIRSpec/G395H transmission spectrum of the 2.2$\,R_\oplus$ TOI-270d ($4.78\,M_\oplus$, $T_\mathrm{eq}$=350-380 K), delivering unprecedented sensitivity for atmospheric characterization in the sub-Neptune regime. We detect five vibrational bands of CH$_4$ at 1.15, 1.4, 1.7, 2.3, and 3.3$\,\mu$m (9.4$\sigma$), the signature of CO$_2$ at 4.3$\,\mu$m (4.8$\sigma$), water vapor (2.5$\sigma$), and potential signatures of SO$_2$ at 4.0$\,\mu \mathrm{m}$ and CS$_2$ at 4.6$\,\mu\mathrm{m}$. Intriguingly, we find an overall highly metal-rich atmosphere, with a mean molecular weight of $5.47_{-1.14}^{+1.25}$. We infer an atmospheric metal mass fraction of $58_{-12}^{+8}\%$ and a C/O of $0.47_{-0.19}^{+0.16}$, indicating that approximately half the mass of the outer envelope is in high-molecular-weight volatiles (H$_2$O, CH$_4$, CO, CO$_2$) rather than H$_2$/He. We introduce a sub-Neptune classification scheme and identify TOI-270d as a "miscible-envelope sub-Neptune" in which H$_2$/He is well-mixed with the high-molecular-weight volatiles in a miscible supercritical metal-rich envelope. For a fully miscible envelope, we conclude that TOI-270d's interior is $90_{-4}^{+3}\,$wt$\,\%$ rock/iron, indicating that it formed as a rocky planet that accreted a few wt % of H$_2$/He, with the overall envelope metal content explained by magma-ocean/envelope reactions without the need for significant ice accretion. TOI-270d may well be an archetype of the overall population of sub-Neptunes., Comment: 25 pages, 12 figures

With the advent of JWST and spectroscopic characterization of exoplanet atmospheres with unprecedented detail, there is a demand for a more complete picture of chemical and photochemical reactions and their impact on atmospheric composition. Traditionally, building reaction networks for (exo)planetary atmospheres involves manually tracking relevant species and reactions, a time-consuming and error-prone process. This approach's applicability is also often limited to specific conditions, making it less versatile for different planetary types. (i.e., photochemical networks for Jupiters may not be directly applicable to water-rich exoplanets). We introduce an automated approach using a computer-aided chemical reaction network generator, combined with a one-dimensional photochemical kinetic-transport model, offering significant advantages. This approach automatically selects reaction rates through a rate-based iterative algorithm and refinement steps, enhancing model reliability. Also, this approach allows for the efficient simulation of diverse chemical environments, from hydrogen to water, carbon dioxide, and nitrogen-dominated atmospheres. Using WASP-39b and WASP-80b as examples, we demonstrate our approach's effectiveness. Our WASP-39b model aligns with prior studies and JWST observations, capturing photochemically produced sulfur dioxide. The WASP-80b model reveals an atmosphere influenced by deep interior thermochemistry and vertical mixing, consistent with JWST NIRCam observations. Furthermore, our model identifies a novel initial step for the N2-NH3-HCN pathway that enhances the conversion efficiency in high-temperature/pressure environments. This automated chemical network generation offers a novel, efficient, and precise framework for studying exoplanetary atmospheres, marking a significant advancement over traditional modeling techniques., Comment: 22 pages, 11 figures, Accepted for Publication in ApJ

A detailed modeling of simultaneous UV-photochemical and thermochemical processes in exoplanet atmosphere-like conditions is essential for the analysis and interpretation of a vast amount of current and future spectral data from exoplanets. However, a detailed reaction kinetic model that incorporates both UV photochemistry and thermal chemistry is challenging due to the massive size of the chemical system as well as to the lack of understanding of photochemistry compared to thermal-only chemistry. Here, we utilize an automatic chemical reaction mechanism generator to build a high-fidelity thermochemical reaction kinetic model later then incorporated with UV-photochemistry enhanced by metastable triplet-state carbon monoxide (a3Pi). Our model results show that two different photochemical reactions driven by Lyman-a photons (i.e. H2 + CO(a3Pi) -> H + HCO and CO(X1Sig+) + CO(a3Pi) -> C(3P) + CO2) can enhance thermal chemistry resulting in significant increases in the formation of CH4, H2O, and CO2 in H2-dominated systems with trace amounts of CO, which qualitatively matches with the observations from previous experimental studies. Our model also suggests that at temperatures above 2000 K, thermal chemistry becomes the dominant process. Finally, the chemistry simulated up to 2500 K does not produce any larger species such as C3 species, benzene or larger (i.e. PAHs). This might indicate that the photochemistry of C2 species such as C2H2 might play a key role in the formation of organic aerosols observed in the previous experimental study., Comment: 58 pages, 17 figures, 4 tables, Manuscript accepted for publication in Astrophysical Journal

Photochemistry is a fundamental process of planetary atmospheres that regulates the atmospheric composition and stability. However, no unambiguous photochemical products have been detected in exoplanet atmospheres to date. Recent observations from the JWST Transiting Exoplanet Early Release Science Program found a spectral absorption feature at 4.05 $\mu$m arising from SO$_2$ in the atmosphere of WASP-39b. WASP-39b is a 1.27-Jupiter-radii, Saturn-mass (0.28 M$_J$) gas giant exoplanet orbiting a Sun-like star with an equilibrium temperature of $\sim$1100 K. The most plausible way of generating SO$_2$ in such an atmosphere is through photochemical processes. Here we show that the SO$_2$ distribution computed by a suite of photochemical models robustly explains the 4.05 $\mu$m spectral feature identified by JWST transmission observations with NIRSpec PRISM (2.7$\sigma$) and G395H (4.5$\sigma$). SO$_2$ is produced by successive oxidation of sulphur radicals freed when hydrogen sulphide (H$_2$S) is destroyed. The sensitivity of the SO$_2$ feature to the enrichment of the atmosphere by heavy elements (metallicity) suggests that it can be used as a tracer of atmospheric properties, with WASP-39b exhibiting an inferred metallicity of $\sim$10$\times$ solar. We further point out that SO$_2$ also shows observable features at ultraviolet and thermal infrared wavelengths not available from the existing observations., Comment: 39 pages, 14 figures, accepted to be published in Nature