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We present the first broadband near- to mid-infrared (3-12 microns) transmission spectrum of the highly-irradiated (T_eq = 981 K) M dwarf rocky planet L 168-9 b (TOI-134 b) observed with the NIRSpec and MIRI instruments aboard JWST. We measure the near-infrared transit depths to a combined median precision of 20 ppm across the three visits in 54 spectroscopic channels with uniform widths of 60 pixels (~0.2 microns wide; R~100), and the mid-infrared transit depths to 61 ppm median precision in 48 wavelength bins (~0.15 microns wide; R~50). We compare the transmission spectrum of L 168-9 b to a grid of 1D thermochemical equilibrium forward models, and rule out atmospheric metallicities of less than 100x solar (mean molecular weights <4 g mol$^{-1}$) to 3-sigma confidence assuming high surface pressure (>1 bar), cloudless atmospheres. Based on photoevaporation models for L 168-9 b with initial atmospheric mass fractions ranging from 2-100%, we find that this planet could not have retained a primordial H/He atmosphere beyond the first 200 Myr of its lifetime. Follow-up MIRI eclipse observations at 15 microns could make it possible to confidently identify a CO2-dominated atmosphere on this planet if one exists., Comment: 19 pages, 11 figures, accepted for publication in The Astronomical Journal

A primary goal of characterizing exoplanet atmospheres is to constrain planetary bulk properties, such as their metallicity, C/O ratio, and intrinsic heat. However, there are significant uncertainties in many aspects of atmospheric physics, such as the strength of vertical mixing. Here we use PICASO and the photochem model to explore how atmospheric chemistry is influenced by planetary properties like metallicity, C/O ratio, $T_{\rm int}$, $T_{\rm eq}$, and $K_{\rm zz}$ in hydrogen-dominated atmospheres. We vary the $T_{\rm eq}$ of the planets between 400 K- 1600 K, across ``cold",``warm," and `hot" objects. We also explore an extensive range of $T_{\rm int}$ values between 30-500 K, representing sub-Neptunes to massive gas giants. We find that gases like CO and CO$_2$ show a drastically different dependence on $K_{\rm zz}$ and C/O for planets with cold interiors (e.g., sub-Neptunes) compared to planets with hotter interiors (e.g., Jupiter mass planets), for the same $T_{\rm eq}$. We also find that gases like CS and CS$_2$ can carry a significant portion of the S- inventory in the upper atmosphere near $T_{\rm eq}$ $\le$ 600 K, below which SO$_2$ ceases to be abundant. For solar C/O, we show that the CO/CH$_4$ ratio in the upper atmospheres of planets can become $\le$1 for planets with low $T_{\rm eq}$, but only if their interiors are cold ($T_{\rm int}$$\le$100 K). We find that photochemical haze precursor molecules in the upper atmosphere show very complex dependence on C/O, $K_{\rm zz}$, $T_{\rm eq}$, and $T_{\rm int}$ for planets with cold interiors (e.g., sub-Neptunes). We also briefly explore fully coupling PICASO and photochem to generate self-consistent radiative-convective-photochemical-equilibrium models., Comment: Revised and re-submitted to ApJ, Main text: Pages 1 to 34, 25 Figures, Appendix: Pages 35 to 36, 1 Figure

The search for life beyond the Solar System remains a primary goal of current and near-future missions, including NASA's upcoming Habitable Worlds Observatory (HWO). However, research into determining the habitability of terrestrial exoplanets has been primarily focused on comparisons to modern-day Earth. Additionally, current characterization strategies focus on the unpolarized flux from these worlds, taking into account only a fraction of the informational content of the reflected light. Better understanding the changes in the reflected light spectrum of the Earth throughout its evolution, as well as analyzing its polarization, will be crucial for mapping its habitability and providing comparison templates to potentially habitable exoplanets. Here we present spectropolarimetric models of the reflected light from the Earth at six epochs across all four geologic eons. We find that the changing surface albedos and atmospheric gas concentrations across the different epochs allow the habitable and non-habitable scenarios to be distinguished, and diagnostic features of clouds and hazes are more noticeable in the polarized signals. We show that common simplifications for exoplanet modeling, including Mie scattering for fractal particles, affect the resulting planetary signals and can lead to non-physical features. Finally, our results suggest that pushing the HWO planet-to-star flux contrast limit down to 1 $\times$ 10$^{-13}$ could allow for the characterization in both unpolarized and polarized light of an Earth-like planet at any stage in its history., Comment: 26 pages, 20 figures. Submitted for publication in The Astrophysical Journal

Exoplanet exploration has revealed that many$\unicode{x2013}$perhaps most$\unicode{x2013}$terrestrial exoplanets formed with substantial H$_2$-rich envelopes, seemingly in contrast to solar system terrestrials, for which there is scant evidence of long-lived primary atmospheres. It is not known how a long-lived primary atmosphere might affect the subsequent habitability prospects of terrestrial exoplanets. Here, we present a new, self-consistent evolutionary model of the transition from primary to secondary atmospheres. The model incorporates all Fe-C-O-H-bearing species and simulates magma ocean solidification, radiative-convective climate, thermal escape, and mantle redox evolution. For our illustrative example TRAPPIST-1, our model strongly favors atmosphere retention for the habitable zone planet TRAPPIST-1e. In contrast, the same model predicts a comparatively thin atmosphere for the Venus-analog TRAPPIST-1b, which would be vulnerable to complete erosion via non-thermal escape and is consistent with JWST observations. More broadly, we conclude that the erosion of primary atmospheres typically does not preclude surface habitability, and frequently results in large surface water inventories due to the reduction of FeO by H$_2$., Comment: Published in Nature Communications. 16 pages, 5 figures

We present a JWST NIRSpec transmission spectrum of the super-Earth exoplanet L 98-59 c. This small (R$_p=1.385\pm0.085$R$_\oplus$, M$_p=2.22\pm0.26$R$_\oplus$), warm (T$_\textrm{eq}=553$K) planet resides in a multi-planet system around a nearby, bright (J = 7.933) M3V star. We find that the transmission spectrum of L 98-59 c is featureless at the precision of our data. We achieve precisions of 22ppm in NIRSpec G395H's NRS1 detector and 36ppm in the NRS2 detector at a resolution R$\sim$200 (30 pixel wide bins). At this level of precision, we are able rule out primordial H$_2$-He atmospheres across a range of cloud pressure levels up to at least $\sim$0.1mbar. By comparison to atmospheric forward models, we also rule out atmospheric metallicities below $\sim$300$\times$ solar at 3$\sigma$ (or equivalently, atmospheric mean molecular weights below $\sim$10~g/mol). We also rule out pure methane atmospheres. The remaining scenarios that are compatible with our data include a planet with no atmosphere at all, or higher mean-molecular weight atmospheres, such as CO$_2$- or H$_2$O-rich atmospheres. This study adds to a growing body of evidence suggesting that planets $\lesssim1.5$R$_\oplus$ lack extended atmospheres., Comment: 21 Pages, 13 Figures; Accepted to AJ

Planets between the sizes of Earth and Neptune are the most common in the Galaxy, bridging the gap between the terrestrial and giant planets in our Solar System. Now that we are firmly in the era of JWST, we can begin to measure, in more detail, the atmospheres of these ubiquitous planets to better understand their evolutionary trajectories. The two planets in the TOI-836 system are ideal candidates for such a study, as they fall on either side of the radius valley, allowing for direct comparisons of the present-day atmospheres of planets that formed in the same environment but had different ultimate end states. We present results from the JWST NIRSpec G395H transit observation of the larger and outer of the planets in this system, TOI-836c (2.587 R$_{\oplus}$, 9.6 M$_{\oplus}$, T$_{\rm eq}$$\sim$665 K). While we measure average 30-pixel binned precisions of $\sim$24ppm for NRS1 and $\sim$43ppm for NRS2 per spectral bin, we do find residual correlated noise in the data, which we attempt to correct using the JWST Engineering Database. We find a featureless transmission spectrum for this sub-Neptune planet, and are able to rule out atmospheric metallicities $<$175$\times$ Solar in the absence of aerosols at $\lesssim$1 millibar. We leverage microphysical models to determine that aerosols at such low pressures are physically plausible. The results presented herein represent the first observation from the COMPASS (Compositions of Mini-Planet Atmospheres for Statistical Study) JWST program, which also includes TOI-836b and will ultimately compare the presence and compositions of atmospheres for 12 super-Earths/sub-Neptunes., Comment: 23 pages, 14 figures, 3 tables, accepted for publication in AJ

We present two transit observations of the ~870K, 1.7R$_E$ super-Earth TOI-836b with JWST NIRSpec/G395H, resulting in a 2.8-5.2$\mu$m transmission spectrum. Using two different reduction pipelines, we obtain a median transit depth precision of 34ppm for Visit 1 and 36ppm for Visit 2, leading to a combined precision of 25ppm in spectroscopic channels 30 pixels wide (~0.02$\mu$m). We find that the transmission spectrum from both visits is well fit by a zero-sloped line by fitting zero-sloped and sloped lines, as well as step functions to our data. Combining both visits, we are able to rule out atmospheres with metallicities <250xSolar for an opaque pressure level of 0.1 bar, corresponding to mean molecular weights to <6gmol$^{-1}$. We therefore conclude that TOI-836b does not have an H$_2$-dominated atmosphere, in possible contrast with its larger, exterior sibling planet, TOI-836c. We recommend that future proposals to observe small planets exercise caution when requiring specific numbers of transits to rule out physical scenarios, particularly for high metallicities and planets around bright host stars, as PandExo predictions appear to be more optimistic than that suggested by the gains from additional transits implied by our data., Comment: 18 pages, 7 figures, 3 tables. Accepted in the Astronomical Journal

Theoretical predictions and observational data indicate a class of sub-Neptune exoplanets may have water-rich interiors covered by hydrogen-dominated atmospheres. Provided suitable climate conditions, such planets could host surface liquid oceans. Motivated by recent JWST observations of K2-18 b, we self-consistently model the photochemistry and potential detectability of biogenic sulfur gases in the atmospheres of temperate sub-Neptune waterworlds for the first time. On Earth today, organic sulfur compounds produced by marine biota are rapidly destroyed by photochemical processes before they can accumulate to significant levels. Domagal-Goldman et al. (2011) suggest that detectable biogenic sulfur signatures could emerge in Archean-like atmospheres with higher biological production or low UV flux. In this study, we explore biogenic sulfur across a wide range of biological fluxes and stellar UV environments. Critically, the main photochemical sinks are absent on the nightside of tidally locked planets. To address this, we further perform experiments with a 3D GCM and a 2D photochemical model (VULCAN 2D (Tsai et al. 2024)) to simulate the global distribution of biogenic gases to investigate their terminator concentrations as seen via transmission spectroscopy. Our models indicate that biogenic sulfur gases can rise to potentially detectable levels on hydrogen-rich waterworlds, but only for enhanced global biosulfur flux ($\gtrsim$20 times modern Earth's flux). We find that it is challenging to identify DMS at 3.4 $\mu m$ where it strongly overlaps with CH$_4$, whereas it is more plausible to detect DMS and companion byproducts, ethylene (C$_2$H$_4$) and ethane (C$_2$H$_6$), in the mid-infrared between 9 and 13 $\mu m$., Comment: 9 pages, 4 figures, accepted for publication in ApJL

JWST recently measured the transmission spectrum of K2-18b, a habitable-zone sub-Neptune exoplanet, detecting CH$_4$ and CO$_2$ in its atmosphere. The discovery paper argued the data are best explained by a habitable "Hycean" world, consisting of a relatively thin H$_2$-dominated atmosphere overlying a liquid water ocean. Here, we use photochemical and climate models to simulate K2-18b as both a Hycean planet and a gas-rich mini-Neptune with no defined surface. We find that a lifeless Hycean world is hard to reconcile with the JWST observations because photochemistry only supports $< 1$ part-per-million CH$_4$ in such an atmosphere while the data suggest about $\sim 1\%$ of the gas is present. Sustaining %-level CH$_4$ on a Hycean K2-18b may require the presence of a methane-producing biosphere, similar to microbial life on Earth $\sim 3$ billion years ago. On the other hand, we predict that a gas-rich mini-Neptune with $100 \times$ solar metallicity should have 4% CH$_4$ and nearly 0.1% CO$_2$, which are compatible with the JWST data. The CH$_4$ and CO$_2$ are produced thermochemically in the deep atmosphere and mixed upward to the low pressures sensitive to transmission spectroscopy. The model predicts H$_2$O, NH$_3$ and CO abundances broadly consistent with the non-detections. Given the additional obstacles to maintaining a stable temperate climate on Hycean worlds due to H$_2$ escape and potential supercriticality at depth, we favor the mini-Neptune interpretation because of its relative simplicity and because it does not need a biosphere or other unknown source of methane to explain the data., Comment: Accepted for publication at ApJL

Chemical disequilibrium quantified via available free energy has previously been proposed as a potential biosignature. However, exoplanet biosignature remote sensing work has not yet investigated how observational uncertainties impact the ability to infer a life-generated available free energy. We pair an atmospheric retrieval tool to a thermodynamics model to assess the detectability of chemical disequilibrium signatures of Earth-like exoplanets, emphasizing the Proterozoic Eon where atmospheric abundances of oxygen-methane disequilibrium pairs may have been relatively high. Retrieval model studies applied across a range of gas abundances revealed that order-of-magnitude constraints on disequilibrium energy are achieved with simulated reflected-light observations at the high abundance scenario and signal-to-noise ratios (50) while weak constraints are found at moderate SNRs (20\,--\,30) for med\,--\,low abundance cases. Furthermore, the disequilibrium energy constraints are improved by modest thermal information encoded in water vapor opacities at optical and near-infrared wavelengths. These results highlight how remotely detecting chemical disequilibrium biosignatures can be a useful and metabolism-agnostic approach to biosignature detection., Comment: Nature Astronomy. Supplementary information see https://zenodo.org/records/10093798 For Source Data see https://zenodo.org/records/8335447

The origin of life on Earth would benefit from a prebiotic atmosphere that produced nitriles, like HCN, which enable ribonucleotide synthesis. However, geochemical evidence suggests that Hadean air was relatively oxidizing with negligible photochemical production of prebiotic molecules. These paradoxes are resolved by iron-rich asteroid impacts that transiently reduced the entire atmosphere, allowing nitriles to form in subsequent photochemistry. Here, we investigate impact-generated reducing atmospheres using new time-dependent, coupled atmospheric chemistry and climate models, which account for gas-phase reactions and surface-catalysis. The resulting H$_2$-, CH$_4$- and NH$_3$-rich atmospheres persist for millions of years, until hydrogen escapes to space. HCN and HCCCN production and rainout to the surface can reach $10^9$ molecules cm$^{-2}$ s$^{-1}$ in hazy atmospheres with a mole ratio of $\mathrm{CH_4} / \mathrm{CO_2} > 0.1$. Smaller $\mathrm{CH_4} / \mathrm{CO_2}$ ratios produce HCN rainout rates $< 10^5$ molecules cm$^{-2}$ s$^{-1}$, and negligible HCCCN. The minimum impactor mass that creates atmospheric $\mathrm{CH_4} / \mathrm{CO_2} > 0.1$ is $4 \times 10^{20}$ to $5 \times 10^{21}$ kg (570 to 1330 km diameter), depending on how efficiently iron reacts with a steam atmosphere, the extent of atmospheric equilibration with an impact-induced melt pond, and the surface area of nickel that catalyzes CH$_4$ production. Alternatively, if steam permeates and deeply oxidizes crust, impactors $\sim 10^{20}$ kg could be effective. Atmospheres with copious nitriles have $> 360$ K surface temperatures, perhaps posing a challenge for RNA longevity, although cloud albedo can produce cooler climates. Regardless, post-impact cyanide can be stockpiled and used in prebiotic schemes after hydrogen has escaped to space., Comment: Accepted by Planetary Science Journal on 7/4/23

Methane has been proposed as an exoplanet biosignature. Imminent observations with the James Webb Space Telescope may enable methane detections on potentially habitable exoplanets, so it is essential to assess in what planetary contexts methane is a compelling biosignature. Methane's short photochemical lifetime in terrestrial planet atmospheres implies that abundant methane requires large replenishment fluxes. While methane can be produced by a variety of abiotic mechanisms such as outgassing, serpentinizing reactions, and impacts, we argue that, in contrast to an Earth-like biosphere, known abiotic processes cannot easily generate atmospheres rich in CH$_4$ and CO$_2$ with limited CO due to the strong redox disequilibrium between CH$_4$ and CO$_2$. Methane is thus more likely to be biogenic for planets with 1) a terrestrial bulk density, high mean-molecular-weight and anoxic atmosphere, and an old host star; 2) an abundance of CH$_4$ that implies surface fluxes exceeding what could be supplied by abiotic processes; and 3) atmospheric CO$_2$ with comparatively little CO., Comment: 10 pages, 5 figures, 15 pages Supplementary Information, 3 Supplementary Figures

Terrestrial planets with large water inventories are likely ubiquitous and will be among the first Earth-sized planets to be characterized with upcoming telescopes. It has previously been argued that waterworlds-particularly those possessing more than 1% H$_2$O-experience limited melt production and outgassing due to the immense pressure overburden of their overlying oceans, unless subject to high internal heating. But an additional, underappreciated obstacle to outgassing on waterworlds is the high solubility of volatiles in high-pressure melts. Here, we investigate this phenomenon and show that volatile solubilities in melts probably prevent almost all magmatic outgassing from waterworlds. Specifically, for Earth-like gravity and oceanic crust composition, oceans or water ice exceeding 10-100 km in depth (0.1-1 GPa) preclude the exsolution of volatiles from partial melt of silicates. This solubility limit compounds the pressure overburden effect as large surface oceans limit both melt production and degassing from any partial melt that is produced. We apply these calculations to Trappist-1 planets to show that, given current mass and radius constraints and implied surface water inventories, Trappist-1f and -1g are unlikely to experience volcanic degassing. While other mechanisms for interior-surface volatile exchange are not completely excluded, the suppression of magmatic outgassing simplifies the range of possible atmospheric evolution trajectories and has implications for interpretation of ostensible biosignature gases, which we illustrate with a coupled model of planetary interior-climate-atmosphere evolution., Comment: 16 pages, 11 figures

Oxygen is a promising exoplanet biosignature due to the evolutionary advantage conferred by harnessing starlight for photosynthesis, and the apparent low likelihood of maintaining oxygen-rich atmospheres without life. Hypothetical scenarios have been proposed for non-biological oxygen accumulation on planets around late M-dwarfs, where the extended pre-main sequence may favor abiotic O$_2$ accumulation. In contrast, abiotic oxygen accumulation on planets around F, G, and K-type stars is seemingly less likely, provided they possess substantial non-condensable gas inventories. The comparative robustness of oxygen biosignatures around larger stars has motivated plans for next-generation telescopes capable of oxygen detection on planets around sun-like stars. However, the general tendency of terrestrial planets to develop oxygen-rich atmospheres across a broad range of initial conditions and evolutionary scenarios has not been explored. Here, we use a coupled thermal-geochemical-climate model of terrestrial planet evolution to illustrate three scenarios whereby significant abiotic oxygen can accumulate around sun-like stars, even when significant non-condensable gas inventories are present. For Earth-mass planets, we find abiotic oxygen can accumulate to modern levels if (1) the CO$_2$:H$_2$O ratio of the initial volatile inventory is high, (2) the initial water inventory exceeds ~50 Earth oceans, or (3) the initial water inventory is very low. Fortunately, these three abiotic oxygen scenarios could be distinguished from biological oxygen with observations of other atmospheric constituents or characterizing the planetary surface. This highlights the need for broadly capable next-generation telescopes that are equipped to constrain surface water inventories via time-resolved photometry and search for temporal biosignatures or disequilibrium biosignatures to assess whether oxygen is biogenic., Comment: Main text 20 pages, 7 figures. Supporting materials 45 pages

The disequilibrium combination of abundant methane and carbon dioxide has been proposed as a promising exoplanet biosignature that is readily detectable with upcoming telescopes such as the James Webb Space Telescope. However, few studies have explored the possibility of non-biological CH4 and CO2 and related contextual clues. Here, we investigate whether magmatic volcanic outgassing on terrestrial planets can produce atmospheric CH4 and CO2 with a thermodynamic model. Our model suggests that volcanoes are unlikely to produce CH4 fluxes comparable to biological fluxes. Improbable cases where volcanoes produce biological amounts of CH4 also produce ample carbon monoxide. We show, using a photochemical model, that high abiotic CH4 abundances produced by volcanoes would be accompanied by high CO abundances, which could be a detectable false positive diagnostic. Overall, when considering known mechanisms for generating abiotic CH4 on terrestrial planets, we conclude that observations of atmospheric CH4 with CO2 are difficult to explain without the presence of biology when the CH4 abundance implies a surface flux comparable to modern Earth's biological CH4 flux. A small or negligible CO abundance strengthens the CH4+CO2 biosignature because life readily consumes atmospheric CO, while reducing volcanic gases likely cause CO to build up in a planet's atmosphere. Furthermore, the difficulty of volcanically-generated CH4-rich atmospheres suitable for an origin of life may favor alternatives such as impact-induced reducing atmospheres., Comment: Accepted by Planetary Science Journal on September 15th, 2020 and Published on October 29th, 2020

Chemical disequilibrium in exoplanetary atmospheres (detectable with remote spectroscopy) can indicate life. The modern Earth's atmosphere-ocean system has a much larger chemical disequilibrium than other solar system planets with atmospheres because of oxygenic photosynthesis. However, no analysis exists comparing disequilibrium on lifeless, prebiotic planets to disequilibrium on worlds with primitive chemotrophic biospheres that live off chemicals and not light. Here, we use a photochemical-microbial ecosystem model to calculate the atmosphere-ocean disequilibria of Earth with no life and with a chemotrophic biosphere. We show that the prebiotic Earth likely had a relatively large atmosphere-ocean disequilibrium due to the coexistence of water and volcanic H2, CO2, and CO. Subsequent chemotrophic life probably destroyed nearly all of the prebiotic disequilibrium through its metabolism, leaving a likely smaller disequilibrium between N2, CO2, CH4, and liquid water. So, disequilibrium fell with the rise of chemotrophic life then later rose with atmospheric oxygenation due to oxygenic photosynthesis. We conclude that big prebiotic disequilibrium between H2 and CO2 or CO and water is an anti-biosignature because these easily metabolized species can be eaten due to redox reactions with low activation energy barriers. However, large chemical disequilibrium can also be a biosignature when the disequilibrium arises from a chemical mixture with biologically insurmountable activation energy barriers, and clearly identifiable biogenic gases. Earth's modern disequilibrium between O2, N2, and liquid water along with minor CH4 is such a case. Thus, the interpretation of disequilibrium requires context. With context, disequilibrium can be used to infer dead or living worlds., Comment: This draft was accepted by Astrophysical Journal on 2/29/20