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Abstract Many sub-Neptune and super-Earth exoplanets are expected to develop metal-enriched atmospheres due to atmospheric loss processes such as photoevaporation or core-powered mass loss. Thermochemical equilibrium calculations predict that at high metallicity and a temperature range of 300–700 K, CO₂becomes the dominant carbon species, and graphite may be the thermodynamically favored condensate under low-pressure conditions. Building on prior laboratory findings that such environments yield organic haze rather than graphite, we measured the transmittance spectra of organic haze analogs and graphite samples and computed their optical constants across the measured wavelength range from 0.4 to 25μm. The organic haze exhibits strong vibrational absorption bands, notably at 3.0, 4.5, and 6.0μm, while graphite shows featureless broadband absorption. The derived optical constants of haze and graphite provide the first data set for organic haze analogs formed in CO₂-rich atmospheres and offer improved applicability over prior graphite data derived from bulk reflectance or ellipsometry. We implemented these optical constants into the Virga and PICASO cloud and radiative transfer models to simulate transit spectra for GJ 1214b. The synthetic spectra with organic hazes reproduce the muted spectral features in the near-infrared observed by Hubble and general trends observed by JWST for GJ 1214b, while graphite models yield flat spectra across the observed wavelengths. This suggests haze features may serve as observational markers of carbon-rich atmospheres, whereas graphite’s opacity could lead to radius overestimation, offering a possible explanation for superpuff exoplanets. Our work supplies essential optical to infrared data for interpreting observations of CO₂-rich exoplanet atmospheres. 

Abstract Super-Earths and sub-Neptunes are the most common exoplanets, with a “radius valley” suggesting that super-Earths may form by shedding sub-Neptunes’ gaseous envelopes. Exoplanets that lie closer to the super-Earth side of the valley are more likely to have lost a significant fraction of their original H/He envelopes and become enriched in heavier elements, with CO₂gaining in abundance. It remains unclear which types of haze would form in such atmospheres, potentially significantly affecting spectroscopic observations. To investigate this, we performed laboratory simulations of two CO₂-rich gas mixtures (with 2000 times solar metallicity at 300 and 500 K). We found that under plasma irradiation organic hazes were produced at both temperatures, with a higher haze production rate at 300 K, probably because condensation occurs more readily at lower temperature. Gas-phase analysis demonstrates the formation of various hydrocarbons, oxygen- and nitrogen-containing species, including reactive gas precursors like C₂H₄, CH₂O, and HCN, for haze formation. The compositional analysis of the haze particles reveals various functional groups and molecular formulas in both samples. The 500 K haze sample has larger average molecular sizes, a higher degree of unsaturation with more double or triple bonds present, and higher nitrogen content incorporated as N–H and C=N bonds, indicating different haze formation pathways. These findings not only improve the haze formation theories in CO₂-rich exoplanet atmospheres but also offer important implications for the interpretation of future observational data. 

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 observations^1–3suggests 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. 

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 Program^2,3found 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 M_J) 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 processes^5,6. 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. 

Abstract Measuring the abundances of carbon and oxygen in exoplanet atmospheres is considered a crucial avenue for unlocking the formation and evolution of exoplanetary systems^1,2. Access to the chemical inventory of an exoplanet requires high-precision observations, often inferred from individual molecular detections with low-resolution space-based^3–5and high-resolution ground-based^6–8facilities. 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. 

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 giants^4–6. It is also one of the most promising species to detect in the secondary atmospheres of terrestrial exoplanets^7–9. 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 identification^10–12. 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 programme^13,14. 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.