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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.more » « less
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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.more » « less
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Abstract Ultra-hot Jupiters (UHJs) are among the best targets for atmospheric characterization at high spectral resolution. Resolving their transmission spectra as a function of orbital phase offers a unique window into the 3D nature of these objects. In this work, we present three transits of the UHJ WASP-121b observed with Gemini-S/IGRINS. For the first time, we measure the phase-dependent absorption signals of CO and H2O in the atmosphere of an exoplanet, and we find that they are different. While the blueshift of CO increases during the transit, the absorption lines of H2O become less blueshifted with phase, and even show a redshift in the second half of the transit. These measurements reveal the distinct spatial distributions of both molecules across the atmospheres of UHJs. Also, we find that the H2O signal is absent in the first quarter of the transit, potentially hinting at cloud formation on the evening terminator of WASP-121b. To further interpret the absorption trails of CO and H2O, as well as the Doppler shifts of Fe previously measured with VLT/ESPRESSO, we compare the data to simulated transits of WASP-121b. To this end, we post-process the outputs of the global circulation models with a 3D Monte-Carlo radiative transfer code. Our analysis shows that the atmosphere of WASP-121b is subject to atmospheric drag, as previously suggested by small hotspot offsets inferred from phase-curve observations. Our study highlights the importance of phase-resolved spectroscopy in unravelling the complex atmospheric structure of UHJs and sets the stage for further investigations into their chemistry and dynamics.more » « less
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Abstract The characterization of young planets (<300 Myr) is pivotal for understanding planet formation and evolution. We present the 3–5μm transmission spectrum of the 17 Myr, Jupiter-size (R∼10R⊕) planet, HIP 67522b, observed with JWST NIRSpec/G395H. To check for spot contamination, we obtain a simultaneousg-band transit with the Southern Astrophysical Research Telescope. The spectrum exhibits absorption features 30%–50% deeper than the overall depth, far larger than expected from an equivalent mature planet, and suggests that HIP 67522b’s mass is <20M⊕irrespective of cloud cover and stellar contamination. A Bayesian retrieval analysis returns a mass constraint of 13.8 ± 1.0M⊕. This challenges the previous classification of HIP 67522b as a hot Jupiter and instead, positions it as a precursor to the more common sub-Neptunes. With a density of <0.10 g cm−3, HIP 67522 b is one of the lowest-density planets known. We find strong absorption from H2O and CO2(≥7σ), a modest detection of CO (3.5σ), and weak detections of H2S and SO2(≃2σ). Comparisons with radiative-convective equilibrium models suggest supersolar atmospheric metallicities and solar-to-subsolar C/O ratios, with photochemistry further constraining the inferred atmospheric metallicity to 3 × 10 solar due to the amplitude of the SO2feature. These results point to the formation of HIP 67522b beyond the water snowline, where its envelope was polluted by icy pebbles and planetesimals. The planet is likely experiencing substantial mass loss (0.01–0.03M⊕Myr−1), sufficient for envelope destruction within a gigayear. This highlights the dramatic evolution occurring within the first 100 Myr of its existence.more » « less
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Abstract The recent inference of sulfur dioxide (SO2) in the atmosphere of the hot (approximately 1,100 K), Saturn-mass exoplanet WASP-39b from near-infrared JWST observations1–3suggests that photochemistry is a key process in high-temperature exoplanet atmospheres4. This is because of the low (<1 ppb) abundance of SO2under thermochemical equilibrium compared with that produced from the photochemistry of H2O and H2S (1–10 ppm)4–9. However, the SO2inference was made from a single, small molecular feature in the transmission spectrum of WASP-39b at 4.05 μm and, therefore, the detection of other SO2absorption bands at different wavelengths is needed to better constrain the SO2abundance. Here we report the detection of SO2spectral features at 7.7 and 8.5 μm in the 5–12-μm transmission spectrum of WASP-39b measured by the JWST Mid-Infrared Instrument (MIRI) Low Resolution Spectrometer (LRS)10. Our observations suggest an abundance of SO2of 0.5–25 ppm (1σrange), consistent with previous findings4. As well as SO2, we find broad water-vapour absorption features, as well as an unexplained decrease in the transit depth at wavelengths longer than 10 μm. Fitting the spectrum with a grid of atmospheric forward models, we derive an atmospheric heavy-element content (metallicity) for WASP-39b of approximately 7.1–8.0 times solar and demonstrate that photochemistry shapes the spectra of WASP-39b across a broad wavelength range.more » « less
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Abstract Close-in giant exoplanets with temperatures greater than 2,000 K (‘ultra-hot Jupiters’) have been the subject of extensive efforts to determine their atmospheric properties using thermal emission measurements from the Hubble Space Telescope (HST) and Spitzer Space Telescope1–3. However, previous studies have yielded inconsistent results because the small sizes of the spectral features and the limited information content of the data resulted in high sensitivity to the varying assumptions made in the treatment of instrument systematics and the atmospheric retrieval analysis3–12. Here we present a dayside thermal emission spectrum of the ultra-hot Jupiter WASP-18b obtained with the NIRISS13instrument on the JWST. The data span 0.85 to 2.85 μm in wavelength at an average resolving power of 400 and exhibit minimal systematics. The spectrum shows three water emission features (at >6σconfidence) and evidence for optical opacity, possibly attributable to H−, TiO and VO (combined significance of 3.8σ). Models that fit the data require a thermal inversion, molecular dissociation as predicted by chemical equilibrium, a solar heavy-element abundance (‘metallicity’,$${\rm{M/H}}=1.0{3}_{-0.51}^{+1.11}$$ times solar) and a carbon-to-oxygen (C/O) ratio less than unity. The data also yield a dayside brightness temperature map, which shows a peak in temperature near the substellar point that decreases steeply and symmetrically with longitude towards the terminators.more » « less
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Abstract Photochemistry is a fundamental process of planetary atmospheres that regulates the atmospheric composition and stability1. However, no unambiguous photochemical products have been detected in exoplanet atmospheres so far. Recent observations from the JWST Transiting Exoplanet Community Early Release Science Program2,3found a spectral absorption feature at 4.05 μm arising from sulfur dioxide (SO2) in the atmosphere of WASP-39b. WASP-39b is a 1.27-Jupiter-radii, Saturn-mass (0.28 MJ) gas giant exoplanet orbiting a Sun-like star with an equilibrium temperature of around 1,100 K (ref. 4). The most plausible way of generating SO2in such an atmosphere is through photochemical processes5,6. Here we show that the SO2distribution computed by a suite of photochemical models robustly explains the 4.05-μm spectral feature identified by JWST transmission observations7with NIRSpec PRISM (2.7σ)8and G395H (4.5σ)9. SO2is produced by successive oxidation of sulfur radicals freed when hydrogen sulfide (H2S) is destroyed. The sensitivity of the SO2feature 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 about 10× solar. We further point out that SO2also shows observable features at ultraviolet and thermal infrared wavelengths not available from the existing observations.more » « less
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Abstract Measuring the abundances of carbon and oxygen in exoplanet atmospheres is considered a crucial avenue for unlocking the formation and evolution of exoplanetary systems1,2. Access to the chemical inventory of an exoplanet requires high-precision observations, often inferred from individual molecular detections with low-resolution space-based3–5and high-resolution ground-based6–8facilities. Here we report the medium-resolution (R ≈ 600) transmission spectrum of an exoplanet atmosphere between 3 and 5 μm covering several absorption features for the Saturn-mass exoplanet WASP-39b (ref. 9), obtained with the Near Infrared Spectrograph (NIRSpec) G395H grating of JWST. Our observations achieve 1.46 times photon precision, providing an average transit depth uncertainty of 221 ppm per spectroscopic bin, and present minimal impacts from systematic effects. We detect significant absorption from CO2(28.5σ) and H2O (21.5σ), and identify SO2as the source of absorption at 4.1 μm (4.8σ). Best-fit atmospheric models range between 3 and 10 times solar metallicity, with sub-solar to solar C/O ratios. These results, including the detection of SO2, underscore the importance of characterizing the chemistry in exoplanet atmospheres and showcase NIRSpec G395H as an excellent mode for time-series observations over this critical wavelength range10.more » « less
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Abstract Measuring the metallicity and carbon-to-oxygen (C/O) ratio in exoplanet atmospheres is a fundamental step towards constraining the dominant chemical processes at work and, if in equilibrium, revealing planet formation histories. Transmission spectroscopy (for example, refs.1,2) provides the necessary means by constraining the abundances of oxygen- and carbon-bearing species; however, this requires broad wavelength coverage, moderate spectral resolution and high precision, which, together, are not achievable with previous observatories. Now that JWST has commenced science operations, we are able to observe exoplanets at previously uncharted wavelengths and spectral resolutions. Here we report time-series observations of the transiting exoplanet WASP-39b using JWST’s Near InfraRed Camera (NIRCam). The long-wavelength spectroscopic and short-wavelength photometric light curves span 2.0–4.0 micrometres, exhibit minimal systematics and reveal well defined molecular absorption features in the planet’s spectrum. Specifically, we detect gaseous water in the atmosphere and place an upper limit on the abundance of methane. The otherwise prominent carbon dioxide feature at 2.8 micrometres is largely masked by water. The best-fit chemical equilibrium models favour an atmospheric metallicity of 1–100-times solar (that is, an enrichment of elements heavier than helium relative to the Sun) and a substellar C/O ratio. The inferred high metallicity and low C/O ratio may indicate significant accretion of solid materials during planet formation (for example, refs.3,4,) or disequilibrium processes in the upper atmosphere (for example, refs.5,6).more » « less
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Abstract Carbon dioxide (CO2) is a key chemical species that is found in a wide range of planetary atmospheres. In the context of exoplanets, CO2is an indicator of the metal enrichment (that is, elements heavier than helium, also called ‘metallicity’)1–3, and thus the formation processes of the primary atmospheres of hot gas giants4–6. It is also one of the most promising species to detect in the secondary atmospheres of terrestrial exoplanets7–9. Previous photometric measurements of transiting planets with the Spitzer Space Telescope have given hints of the presence of CO2, but have not yielded definitive detections owing to the lack of unambiguous spectroscopic identification10–12. Here we present the detection of CO2in the atmosphere of the gas giant exoplanet WASP-39b from transmission spectroscopy observations obtained with JWST as part of the Early Release Science programme13,14. The data used in this study span 3.0–5.5 micrometres in wavelength and show a prominent CO2absorption feature at 4.3 micrometres (26-sigma significance). The overall spectrum is well matched by one-dimensional, ten-times solar metallicity models that assume radiative–convective–thermochemical equilibrium and have moderate cloud opacity. These models predict that the atmosphere should have water, carbon monoxide and hydrogen sulfide in addition to CO2, but little methane. Furthermore, we also tentatively detect a small absorption feature near 4.0 micrometres that is not reproduced by these models.more » « less
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