Search

Our interpretation of terrestrial exoplanet atmospheric spectra will always be limited by the accuracy of the data we use as input in our forward and retrieval models. Ultraviolet molecular absorption cross sections are one category of these essential model inputs; however, they are often poorly characterized at the longest wavelengths relevant to photo-dissociation. Photolysis reactions dominate the chemical kinetics of temperate terrestrial planet atmospheres. One molecule of particular importance is CO$_2$, which is likely present in all terrestrial planet atmospheres. The photolysis of CO$_2$ can introduce CO and O, as well as shield tropospheric water vapor from undergoing photolysis. This is important because H$_2$O photolysis produces OH, which serves as a major reactive sink to many atmospheric trace gases. Here, we construct CO$_2$ cross-section prescriptions at 195K and 300K extrapolated beyond 200 nm from measured cross sections. We compare results from the implementation of these new cross sections to the most commonly used CO$_2$ prescriptions for temperate, terrestrial planets with Archean-like atmospheres. We generally find that the observational consequences of CO$_2$ dissociation beyond 200 nm is minimal so long as our least conservative (highest opacity) prescription can be ruled out. Moreover, implementing our recommended extended CO$_2$ cross sections does not substantially alter previous results showing the consequential photochemical impact of extended H$_2$O cross sections., Comment: 24 pages, 21 figures, 3 tables. Published in the Astrophysical Journal

JWST has created a new era of terrestrial exoplanet atmospheric characterization, and with it the possibility to detect potential biosignature gases like CH$_{4}$. Our interpretation of exoplanet atmospheric spectra, and the veracity of these interpretations, will be limited by our understanding of atmospheric processes and the accuracy of input modeling data. Molecular cross-sections are essential inputs to these models. The photochemistry of temperate planets depends on photolysis reactions whose rates are governed by the dissociation cross-sections of key molecules. H$_{2}$O is one such molecule; the photolysis of H$_{2}$O produces OH, a highly reactive and efficient sink for atmospheric trace gases. We investigate the photochemical effects of improved H$_{2}$O cross-sections on anoxic terrestrial planets as a function of host star spectral type (FGKM) and CH$_{4}$ surface flux. Our results show that updated H$_{2}$O cross-sections, extended to wavelengths $>$200 nm, substantially impact the predicted abundances of trace gases destroyed by OH. The differences for anoxic terrestrial planets orbiting Sun-like host stars are greatest, showing changes of up to three orders of magnitude in surface CO levels, and over an order of magnitude in surface CH$_{4}$ levels. These differences lead to observable changes in simulated planetary spectra, especially important in the context of future direct-imaging missions. In contrast, the atmospheres of planets orbiting M-dwarf stars are substantially less affected. Our results demonstrate a pressing need for refined dissociation cross-section data for H$_{2}$O, where uncertainties remain, and other key molecules, especially at mid-UV wavelengths $>$200 nm., Comment: 25 pages, 20 figures, 2 tables. Published in ApJ

Long-standing unexplained Venus atmosphere observations and chemical anomalies point to unknown chemistry but also leave room for the possibility of life. The unexplained observations include several gases out of thermodynamic equilibrium (e.g. tens of ppm O2, the possible presence of PH3 and NH3, SO2 and H2O vertical abundance profiles), an unknown composition of large, lower cloud particles, and the "unknown absorber(s)". Here we first review relevant properties of the Venus atmosphere and then describe the atmospheric chemical anomalies and how they motivate future astrobiology missions to Venus., Comment: Published in Astrobiology (in press); Partially based on the text of the Venus Life Finder Mission Study report (arXiv:2112.05153)

Ultra-cool dwarf stars are abundant, long-lived, and uniquely suited to enable the atmospheric study of transiting terrestrial companions with JWST. Amongst them, the most prominent is the M8.5V star TRAPPIST-1 and its seven planets. While JWST Cycle 1 observations have started to yield preliminary insights into the planets, they have also revealed that their atmospheric exploration requires a better understanding of their host star. Here, we propose a roadmap to characterize the TRAPPIST-1 system -- and others like it -- in an efficient and robust manner. We notably recommend that -- although more challenging to schedule -- multi-transit windows be prioritized to mitigate the effects of stellar activity and gather up to twice more transits per JWST hour spent. We conclude that, for such systems, planets cannot be studied in isolation by small programs, but rather need large-scale, jointly space- and ground-based initiatives to fully exploit the capabilities of JWST for the exploration of terrestrial planets.

Clouds are prevalent in many of the exoplanet atmospheres that have been observed to date. For transiting exoplanets, we know if clouds are present because they mute spectral features and cause wavelength-dependent scattering. While the exact composition of these clouds is largely unknown, this information is vital to understanding the chemistry and energy budget of planetary atmospheres. In this work, we observe one transit of the hot Jupiter WASP-17b with JWST's MIRI LRS and generate a transmission spectrum from 5-12 $\rm{\mu}$m. These wavelengths allow us to probe absorption due to the vibrational modes of various predicted cloud species. Our transmission spectrum shows additional opacity centered at 8.6 $\rm{\mu}$m, and detailed atmospheric modeling and retrievals identify this feature as SiO$_2$(s) (quartz) clouds. The SiO$_2$(s) clouds model is preferred at 3.5-4.2$\sigma$ versus a cloud-free model and at 2.6$\sigma$ versus a generic aerosol prescription. We find the SiO$_2$(s) clouds are comprised of small ${\sim}0.01$ $\rm{\mu}$m particles, which extend to high altitudes in the atmosphere. The atmosphere also shows a depletion of H$_2$O, a finding consistent with the formation of high-temperature aerosols from oxygen-rich species. This work is part of a series of studies by our JWST Telescope Scientist Team (JWST-TST), in which we will use Guaranteed Time Observations to perform Deep Reconnaissance of Exoplanet Atmospheres through Multi-instrument Spectroscopy (DREAMS)., Comment: 19 pages, 7 figures, fixed typo in Equation 3

Efforts to spectrally characterize the atmospheric compositions of temperate terrestrial exoplanets orbiting M-dwarf stars with the James Webb Space Telescope (JWST) are now underway. Key molecular targets of such searches include O$_2$ and CO, which are potential indicators of life. Recently, it was proposed that CO$_2$ photolysis generates abundant ($\gtrsim0.1$ bar) abiotic O$_2$ and CO in the atmospheres of habitable M-dwarf planets with CO$_2$-rich atmospheres, constituting a strong false positive for O$_2$ as a biosignature and further complicating efforts to use CO as a diagnostic of surface biology. Importantly, this implied that TRAPPIST-1e and TRAPPIST-1f, now under observation with JWST, would abiotically accumulate abundant O$_2$ and CO, if habitable. Here, we use a multi-model approach to re-examine photochemical O$_2$ and CO accumulation on planets orbiting M-dwarf stars. We show that photochemical O$_2$ remains a trace gas on habitable CO$_2$-rich M-dwarf planets, with earlier predictions of abundant O$_2$ and CO due to an atmospheric model top that was too low to accurately resolve the unusually-high CO$_2$ photolysis peak on such worlds. Our work strengthens the case for O$_2$ as a biosignature gas, and affirms the importance of CO as a diagnostic of photochemical O$_2$ production. However, observationally relevant false positive potential remains, especially for O$_2$'s photochemical product O$_3$, and further work is required to confidently understand O$_2$ and O$_3$ as biosignature gases on M-dwarf planets., Comment: Accepted to Astrophysical Journal Letters (in press). 3 Figures, 1 Table in main text; 4 Figures, 5 Tables in SI

Characterizing rocky exoplanet atmospheres is a key goal of exoplanet science, but interpreting such observations will require understanding the stellar UV irradiation incident on the planet from its host star. Stellar UV mediates atmospheric escape, photochemistry, and planetary habitability, and observations of rocky exoplanets can only be understood in the context of the UV SED of their host stars. Particularly important are SEDs from observationally favorable but poorly understood low-mass M-dwarf stars, which are the only plausible targets for rocky planet atmospheric characterization for the next 1-2 decades. In this work, we explore the utility of AstroSat UVIT for the characterization of the UV SEDs of low-mass stars. We present observations of the nearby M0 star HIP 23309 in the FUV and NUV gratings of UVIT. Our FUV spectra are consistent with contemporaneous HST data and our NUV spectra are stable between orbits, suggesting UVIT is a viable tool for the characterization of the SEDs of low-mass stars. We apply our measured spectra to simulations of photochemistry and habitability for a hypothetical rocky planet orbiting HIP 23309 and elucidate the utility and limitations of UVIT in deriving UV SEDs of M-dwarf exoplanet hosts. Our work validates UVIT as a tool to complement HST in the characterization of exoplanet host stars and carries implications for its successor missions like INSIST., Comment: Accepted to AJ

Phosphorus (III) oxide (P$_4$O$_6$) has been suggested to be a major component of the gas phase phosphorus chemistry in the atmospheres of gas giant planets and of Venus. However, P$_4$O$_6$'s proposed role is based on thermodynamic modeling, itself based on values for the free energy of formation of P$_4$O$_6$ estimated from limited experimental data. Values of the standard Gibbs free energy of formation ($\Delta$Go(g)) of P$_4$O$_6$ in the literature differ by up to ~656 kJ/mol, a huge range. Depending on which value is assumed, P$_4$O$_6$ may either be the majority phosphorus species present or be completely absent from modeled atmospheres. Here, we critically review the literature thermodynamic values and compare their predictions to observed constraints on P$_4$O$_6$ geochemistry. We conclude that the widely used values from the NIST/JANAF database are almost certainly too low (predicting that P$_4$O$_6$ is more stable than is plausible). We show that, regardless of the value of $\Delta$Go(g) for P$_4$O$_6$ assumed, the formation of phosphine from P$_4$O$_6$ in the Venusian atmosphere is thermodynamically unfavorable. We conclude that there is a need for more robust data on both the thermodynamics of phosphorus chemistry for astronomical and geological modeling in general and for understanding the atmosphere of Venus and the gas giant planets in particular., Comment: Article published in ACS Earth Space Chem. https://pubs.acs.org/doi/full/10.1021/acsearthspacechem.3c00016

The search for signs of life on other worlds has largely focused on terrestrial planets. Recent work, however, argues that life could exist in the atmospheres of temperate sub-Neptunes. Here, we evaluate the usefulness of carbon dioxide isotopologues as evidence of aerial life. Carbon isotopes are of particular interest as metabolic processes preferentially use the lighter $^{12}$C over $^{13}$C. In principle, the upcoming James Webb Space Telescope (JWST) will be able to spectrally resolve the $^{12}$C and $^{13}$C isotopologues of CO$_{2}$, but not CO and CH$_{4}$. We simulated observations of CO$_{2}$ isotopologues in the H$_{2}$-dominated atmospheres of our nearest ($< 40$ pc), temperate (equilibrium temperature of 250-350 K) sub-Neptunes with M dwarf host stars. We find $^{13}$CO$_{2}$ and $^{12}$CO$_{2}$ distinguishable if the atmosphere is H$_{2}$-dominated with a few percentage points of CO$_{2}$ for the most idealized target with an Earth-like composition of the two most abundant isotopologues, $^{12}$CO$_{2}$ and $^{13}$CO$_{2}$. With a Neptune-like metallicity of 100$\times$ solar and a C/O of 0.55, we are unable to distinguish between $^{13}$CO$_{2}$ and $^{12}$CO$_{2}$ in the atmospheres of temperate sub-Neptunes. If atmospheric composition largely follows metallicity scaling, the concentration of CO$_{2}$ in a H$_{2}$-dominated atmosphere will be too low to distinguish CO$_{2}$ isotopologues with JWST. In contrast, at higher metallicities, there will be more CO$_{2}$, but the smaller atmospheric scale height makes the measurement impossible. Carbon dioxide isotopologues are unlikely to be useful biosignature gases for the JWST era. Instead, isotopologue measurements should be used to evaluate formation mechanisms of planets and exoplanetary systems., Comment: 11 pages, 3 figures. Published in the Astrophysical Journal on May 4, 2022. The final authenticated version is available online at: https://iopscience.iop.org/article/10.3847/1538-4357/ac625f/meta

About 2.5 billion years ago, microbes learned to harness plentiful solar energy to reduce CO$_2$ with H$_2$O, extracting energy and producing O$_2$ as waste. O$_2$ production from this metabolic process was so vigorous that it saturated its photochemical sinks, permitting it to reach "runaway" conditions and rapidly accumulate in the atmosphere despite its reactivity. Here we argue that O$_2$ may not be unique: diverse gases produced by life may experience a "runaway" effect similar to O$_2$. This runaway occurs because the ability of an atmosphere to photochemically cleanse itself of trace gases is generally finite. If produced at rates exceeding this finite limit, even reactive gases can rapidly accumulate to high concentrations and become potentially detectable. Planets orbiting smaller, cooler stars, such as the M dwarfs that are the prime targets for the James Webb Space Telescope (JWST), are especially favorable for runaway due to their lower UV emission compared to higher-mass stars. As an illustrative case study, we show that on a habitable exoplanet with an H$_2$-N$_2$ atmosphere and net surface production of NH$_3$ orbiting an M dwarf (the "Cold Haber World" scenario), the reactive biogenic gas NH$_3$ can enter runaway, whereupon an increase in the surface production flux of one order of magnitude can increase NH$_3$ concentrations by three orders of magnitude and render it detectable by JWST in just two transits. Our work on this and other gases suggests that diverse signs of life on exoplanets may be readily detectable at biochemically plausible production rates., Comment: In press at ApJ (2022). Code available via GitHub; see Acknowledgements section for details and URLs. Comments & feedback welcome

Following the discovery of the first exoplanet candidate transiting a white dwarf (WD), a "white dwarf opportunity" for characterizing the atmospheres of terrestrial exoplanets around WDs is emerging. Large planet-to-star size ratios and hence large transit depths make transiting WD exoplanets favorable targets for transmission spectroscopy - conclusive detection of spectral features on an Earth-like planet transiting a close-by WD can be achieved within a medium James Webb Space Telescope (JWST) program. Despite the apparently promising opportunity, however, the post-main sequence (MS) evolutionary history of a first-generation WD exoplanet has never been incorporated in atmospheric modeling. Furthermore, second-generation planets formed in WD debris disks have never been studied from a photochemical perspective. We demonstrate that transmission spectroscopy can identify a second-generation rocky WD exoplanet with a thick ($\sim1$ bar) H$_2$-dominated atmosphere. In addition, we can infer outgassing activities of a WD exoplanet based on its transmission spectra and test photochemical runaway by studying CH$_4$ buildup., Comment: 25 pages, 10 figures, 3 tables, accepted for publication in ApJ Letters

The initial reports of the presence of phosphine in the cloud decks of Venus has led to the suggestion that volcanism was the source of phosphine, through volcanic phosphides ejected into the clouds. Here we examine the idea that mantle plume volcanism, bringing material from the deep mantle to the surface, could generate observed amounts of phosphine through interaction of explosively erupted phosphide with sulfuric acid clouds. Direct eruption of deep mantle phosphide is unphysical, but shallower material could contain traces of phosphide, and could be erupted to the surface. Explosive eruption that efficiently transported material to the clouds would require ocean:magma interactions or subduction of hydrated oceanic crust, neither of which occur on modern Venus. The transport of erupted material to altitudes coinciding with the observations of phosphine is consequently very inefficient. Using the model proposed by Truong and Lunine as a base case, we estimate that an eruption volume of at least 21,600 km3/year would be required to explain the presence of 1 ppb phosphine in the clouds. This is greater than any historical terrestrial eruption rate, and would have several detectable consequences for remote and in situ observations to confirm. More realistic lithospheric mineralogy, volcano mechanics or atmospheric photochemistry require even more volcanism., Comment: The paper expands on and confirms the results of Bains et al. 2021 arXiv:2009.06499 and provides further constrains on the model of the production of phosphine on Venus proposed by Truong and Lunine https://www.pnas.org/content/118/29/e2021689118 ; v2 is published in Universe

The potential detection of ppb levels phosphine (PH3) in the clouds of Venus through millimeter-wavelength astronomical observations is extremely surprising as PH3 is an unexpected component of an oxidized environment of Venus. A thorough analysis of potential sources suggests that no known process in the consensus model of Venus' atmosphere or geology could produce PH3 at anywhere near the observed abundance. Therefore, if the presence of PH3 in Venus' atmosphere is confirmed, it is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The source of atmospheric PH3 could be unknown geo- or photochemistry, which would imply that the consensus on Venus' chemistry is significantly incomplete. An even more extreme possibility is that strictly aerial microbial biosphere produces PH3. This paper summarizes the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection one year ago., Comment: A short overview of the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection in September 2020. Additional discussion of possible non-canonical sources of PH3 on Venus is also included. arXiv admin note: text overlap with arXiv:2009.06499

Ultraviolet (UV) light plays a key role in surficial theories of the origin of life, and numerous studies have focused on constraining the atmospheric transmission of UV radiation on early Earth. However, the UV transmission of the natural waters in which origins-of-life chemistry (prebiotic chemistry) is postulated to have occurred is poorly constrained. In this work, we combine laboratory and literature-derived absorption spectra of potential aqueous-phase prebiotic UV absorbers with literature estimates of their concentrations on early Earth to constrain the prebiotic UV environment in marine and terrestrial natural waters, and consider the implications for prebiotic chemistry. We find that prebiotic freshwaters were largely transparent in the UV, contrary to assumptions by some models of prebiotic chemistry. Some waters, e.g., high-salinity waters like carbonate lakes, may be deficient in shortwave ($\leq220$ nm) UV flux. More dramatically, ferrous waters can be strongly UV-shielded, particularly if the Fe$^{2+}$ forms highly UV-absorbent species like Fe(CN)$_6^{4-}$. Such waters may be compelling venues for UV-averse origin-of-life scenarios, but are disfavorable for some UV-dependent prebiotic chemistries. UV light can trigger photochemistry even if attenuated through photochemical transformations of the absorber (e.g., $e^{-}_{aq}$ production from halide irradiation), which may have both constructive and destructive effects for prebiotic syntheses. Prebiotic chemistries invoking waters containing such absorbers must self-consistently account for the chemical effects of these transformations. The speciation and abundance of Fe$^{2+}$ in natural waters on early Earth is a major uncertainty, and should be prioritized for further investigation as it plays a major role in UV transmission in prebiotic natural waters., Comment: Accepted to Astrobiology. Associated measurements/code: https://github.com/sukritranjan/dirty-water-1/. Comments solicited

New analysis is presented of the 1.1 mm wavelength absorption lines in Venus' atmosphere that suggested the presence of phosphine. We retrieve a sulphur dioxide observation from the JCMT archive that was simultaneous within a few days of the PH3 1-0 spectrum obtained in June 2017, and demonstrate via a radiative transfer calculation that contamination of PH3 by SO2 was ~10 per cent. We also present ALMA 2019 spectra of PH3 1-0 and an SO2 transition acquired simultaneously, and infer that SO2 line-contamination was ~2 percent (for the least-noisy half of the planetary disc). The contamination-subtracted ALMA and JCMT spectra (of 6-8 sigma confidence) are now consistent with similar absorption-depths at the two epochs. The two values span -1.9(+/-0.2) 10-4 of the continuum signal (which was re-estimated for ALMA), albeit for differing planetary areas. This suggests that the abundance attributed to phosphine in Venus' atmosphere was broadly similar in 2017 and 2019., Comment: v3 is an proofread version of the paper that will appear in print in MNRAS

The study of origins of life on Earth and the search for life on other planets are closely linked. Prebiotic chemical scenarios can help prioritize planets as targets for the search for life as we know it and can provide informative priors to help us assess the likelihood that particular spectroscopic features are evidence of life. The prerequisites for origins scenarios themselves predict spectral signatures. The interplay between origins research and the search for extraterrestrial life must start with lab work guiding exploratory ventures in the solar system, and the discoveries in the solar system informing future exoplanet observations and laboratory research. Subsequent exoplanet research will in turn provide statistical context to conclusions about the nature and origins of life., Comment: To be published as article 7 in the "Geoscience Beyond the Solar System" issue of Elements magazine, v17 No4

Ammonia (NH3) in a terrestrial planet atmosphere is generally a good biosignature gas, primarily because terrestrial planets have no significant known abiotic NH3 source. The conditions required for NH3 to accumulate in the atmosphere are, however, stringent. NH3's high water solubility and high bio-useability likely prevent NH3 from accumulating in the atmosphere to detectable levels unless life is a net source of NH3 and produces enough NH3 to saturate the surface sinks. Only then can NH3 accumulate in the atmosphere with a reasonable surface production flux. For the highly favorable planetary scenario of terrestrial planets with H2-dominated atmospheres orbiting M dwarf stars (M5V), we find a minimum of about 5 ppm column-averaged mixing ratio is needed for NH3 to be detectable with JWST, considering a 10 ppm JWST systematic noise floor. When the surface is saturated with NH3 (i.e., there are no NH3-removal reactions on the surface), the required biological surface flux to reach 5 ppm is on the order of 10^10 molecules cm-2 s-1, comparable to the terrestrial biological production of CH4. However, when the surface is unsaturated with NH3, due to additional sinks present on the surface, life would have to produce NH3 at surface flux levels on the order of 10^15 molecules cm-2 s-1 (approx. 4.5x10^6 Tg year-1). This value is roughly 20,000 times greater than the biological production of NH3 on Earth and about 10,000 times greater than Earth's CH4 biological production. Volatile amines have similar solubilities and reactivities to NH3 and hence share NH3's weaknesses and strengths as a biosignature. Finally, to establish NH3 as a biosignature gas, we must rule out mini-Neptunes with deep atmospheres, where temperatures and pressures are high enough for NH3's atmospheric production., Comment: under revision, submitted to Astrobiology on 18-Aug-2020

We recover PH3 in the atmosphere of Venus in data taken with ALMA, using three different calibration methods. The whole-planet signal is recovered with 5.4{\sigma} confidence using Venus bandpass self-calibration, and two simpler approaches are shown to yield example 4.5-4.8{\sigma} detections of the equatorial belt. Non-recovery by Villanueva et al. is attributable to (a) including areas of the planet with high spectral-artefacts and (b) retaining all antenna baselines which raises the noise by a factor ~2.5. We release a data-processing script that enables our whole-planet result to be reproduced. The JCMT detection of PH3 remains robust, with the alternative SO2 attribution proposed by Villanueva et al. appearing inconsistent both in line-velocity and with millimetre-wavelength SO2 monitoring. SO2 contamination of the ALMA PH3-line is minimal. Net abundances for PH3, in the gas column above ~55 km, are up to ~20 ppb planet-wide with JCMT, and ~7 ppb with ALMA (but with signal-loss possible on scales approaching planetary size). Derived abundances will differ if PH3 occupies restricted altitudes - molecules in the clouds will contribute significantly less absorption at line-centre than equivalent numbers of mesospheric molecules - but in the latter zone, PH3 lifetime is expected to be short. Given we recover phosphine, we suggest possible solutions (requiring substantial further testing): a small collisional broadening coefficient could give narrow lines from lower altitude, or a high eddy diffusion coefficient could allow molecules to survive longer at higher altitudes. Alternatively, PH3 could be actively produced by an unknown mechanism in the mesosphere, but this would need to be in addition to cloud-level PH3 detected retrospectively by Pioneer-Venus., Comment: Revised and updated re-analysis of the phosphine spectra in Venus' clouds; Submitted to Nature Astronomy "Matters Arising" on Apr/19/2021

Research for possible biosignature gases on habitable exoplanet atmosphere is accelerating. We add isoprene, C5H8, to the roster of biosignature gases. We found that formation of isoprene geochemical formation is highly thermodynamically disfavored and has no known abiotic false positives. The isoprene production rate on Earth rivals that of methane (~ 500 Tg yr-1). On Earth, isoprene is rapidly destroyed by oxygen-containing radicals, but its production is ubiquitous to a diverse array of evolutionarily distant organisms, from bacteria to plants and animals-few, if any at all, volatile secondary metabolite has a larger evolutionary reach. While non-photochemical sinks of isoprene may exist, the destruction of isoprene in an anoxic atmosphere is mainly driven by photochemistry. Motivated by the concept that isoprene might accumulate in anoxic environments, we model the photochemistry and spectroscopic detection of isoprene in habitable temperature, rocky exoplanet anoxic atmospheres with a variety of atmosphere compositions under different host star UV fluxes. Limited by an assumed 10 ppm instrument noise floor, habitable atmosphere characterization using JWST is only achievable with transit signal similar or larger than that for a super-Earth sized exoplanet transiting an M dwarf star with an H2-dominated atmosphere. Unfortunately, isoprene cannot accumulate to detectable abundance without entering a run-away phase, which occurs at a very high production rate, ~ 100 times Earth's production rate. In this run-away scenario isoprene will accumulate to > 100 ppm and its spectral features are detectable with ~ 20 JWST transits. One caveat is that some spectral features are hard to be distinguished from that of methane. Despite these challenges, isoprene is worth adding to the menu of potential biosignature gases., Comment: 62 pages, 24 figures

We published spectra of phosphine molecules in Venus' clouds, following open-science principles in releasing data and scripts (with community input leading to ALMA re-processing, now benefiting multiple projects). Some misconceptions about de-trending of spectral baselines have also emerged, which we address here. Using the JCMT PH3-discovery data, we show that mathematically-correct polynomial fitting of periodic ripples does not lead to "fake lines" (probability < ~1%). We then show that the ripples can be characterised in a non-subjective manner via Fourier transforms. A 20 ppb PH3 feature is ~5{\sigma} compared to the JCMT baseline-uncertainty, and is distinctive as a narrow perturber of the periodic ripple pattern. The structure of the FT-derived baseline also shows that polynomial fitting, if unguided, can amplify artefacts and so artificially reduce significance of real lines., Comment: Response to: Snellen I. et al. Astron. Astroph., in press, arXiv:2010:09761 (2020); Villanueva G. et al. Nat. Ast. Matters Arising; arXiv:2010.14305 (2020); Thompson M. Mon. Not. Roy. Astron. Soc., in press, arXiv:2010.15118 (2020); Submitted to Nature Astronomy "Matters Arising" on Dec/10/2020

Measurements of trace-gases in planetary atmospheres help us explore chemical conditions different to those on Earth. Our nearest neighbor, Venus, has cloud decks that are temperate but hyper-acidic. We report the apparent presence of phosphine (PH3) gas in Venusian atmosphere, where any phosphorus should be in oxidized forms. Single-line millimeter-waveband spectral detections (quality up to ~15 sigma) from the JCMT and ALMA telescopes have no other plausible identification. Atmospheric PH3 at ~20 parts-per-billion abundance is inferred. The presence of phosphine is unexplained after exhaustive study of steady-state chemistry and photochemical pathways, with no currently-known abiotic production routes in Venusian atmosphere, clouds, surface and subsurface, or from lightning, volcanic or meteoritic delivery. Phosphine could originate from unknown photochemistry or geochemistry, or, by analogy with biological production of phosphine on Earth, from the presence of life. Other PH3 spectral features should be sought, while in-situ cloud and surface sampling could examine sources of this gas.

We revisit the hypothesis that there is life in the Venusian clouds to propose a life cycle that resolves the conundrum of how life can persist aloft for hundreds of millions to billions of years. Most discussions of an aerial biosphere in the Venus atmosphere temperate layers never address whether the life-small microbial-type particles-is free floating or confined to the liquid environment inside cloud droplets. We argue that life must reside inside liquid droplets such that it will be protected from a fatal net loss of liquid to the atmosphere, an unavoidable problem for any free-floating microbial life forms. However, the droplet habitat poses a lifetime limitation: Droplets inexorably grow (over a few months) to large enough sizes that are forced by gravity to settle downward to hotter, uninhabitable layers of the Venusian atmosphere. (Droplet fragmentation-which would reduce particle size-does not occur in Venusian atmosphere conditions.) We propose for the first time that the only way life can survive indefinitely is with a life cycle that involves microbial life drying out as liquid droplets evaporate during settling, with the small desiccated 'spores' halting at, and partially populating, the Venus atmosphere stagnant lower haze layer (33-48 km altitude). We, thus, call the Venusian lower haze layer a 'depot' for desiccated microbial life. The spores eventually return to the cloud layer by upward diffusion caused by mixing induced by gravity waves, act as cloud condensation nuclei, and rehydrate for a continued life cycle. We also review the challenges for life in the extremely harsh conditions of the Venusian atmosphere, refuting the notion that the 'habitable' cloud layer has an analogy in any terrestrial environment., Comment: Open Access Astrobiology Article

The recent candidate detection of ~1 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphorus-containing species have not been modelled for Venus' atmosphere before and our work represents the first attempt to model phosphorus species in the Venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a Venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other non-equilibrium processes. None of these potential phosphine production pathways are sufficient to explain the presence of ppb phosphine levels on Venus. If PH3's presence in Venus' atmosphere is confirmed, it therefore is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates in situ follow up sampling missions to Venus. Our analysis provides a template for investigation of phosphine as a biosignature on other worlds., Comment: v2 is in press in Astrobiology, Special Collection: Venus; v2 also expands on the potential of phosphides from the deep mantle volcanism as a source of PH3 (as suggested by Truong and Lunine 2021: https://www.pnas.org/content/118/29/e2021689118) and shows the volcanic source of PH3 to be unlikely

We present a study of the photochemistry of abiotic habitable planets with anoxic CO$_2$-N$_2$ atmospheres. Such worlds are representative of early Earth, Mars and Venus, and analogous exoplanets. H$_2$O photodissociation controls the atmospheric photochemistry of these worlds through production of reactive OH, which dominates the removal of atmospheric trace gases. The near-UV (NUV; $>200$ nm) absorption cross-sections of H$_2$O play an outsized role in OH production; these cross-sections were heretofore unmeasured at habitable temperatures ($<373$ K). We present the first measurements of NUV H$_2$O absorption at $292$ K, and show it to absorb orders of magnitude more than previously assumed. To explore the implications of these new cross-sections, we employ a photochemical model; we first intercompare it with two others and resolve past literature disagreement. The enhanced OH production due to these higher cross-sections leads to efficient recombination of CO and O$_2$, suppressing both by orders of magnitude relative to past predictions and eliminating the low-outgassing "false positive" scenario for O$_2$ as a biosignature around solar-type stars. Enhanced [OH] increases rainout of reductants to the surface, relevant to prebiotic chemistry, and may also suppress CH$_4$ and H$_2$; the latter depends on whether burial of reductants is inhibited on the underlying planet, as is argued for abiotic worlds. While we focus on CO$_2$-rich worlds, our results are relevant to anoxic planets in general. Overall, our work advances the state-of-the-art of photochemical models by providing crucial new H$_2$O cross-sections and resolving past disagreement in the literature, and suggests that detection of spectrally active trace gases like CO in rocky exoplanet atmospheres may be more challenging than previously considered., Comment: Manuscript (this version) accepted to ApJ. Cross-section data available at https://github.com/sukritranjan/ranjanschwietermanharman2020. Feedback continues to be solicited

A long-term goal of exoplanet studies is the identification and detection of biosignature gases. Beyond the most discussed biosignature gas O$_2$, only a handful of gases have been considered in detail. Here we evaluate phosphine (PH$_3$). On Earth, PH$_3$ is associated with anaerobic ecosystems, and as such is a potential biosignature gas on anoxic exoplanets. We simulate CO$_2-$ and H$_2-$dominated habitable terrestrial planet atmospheres. We find that PH$_3$ can accumulate to detectable concentrations on planets with surface production fluxes of 10$^{10}$-10$^{14}$ cm$^{-2}$ s$^{-1}$ (corresponding to surface concentrations of 10s of ppb to 100s of ppm), depending on atmospheric composition and UV flux. While high, such surface fluxes are comparable to the global terrestrial production rate of CH$_4$ (10$^{11}$ cm$^{-2}$ s$^{-1}$) and below the maximum local terrestrial PH$_3$ production rate (10$^{14}$ cm$^{-2}$ s$^{-1}$). As with other gases, PH$_3$ can more readily accumulate on low-UV planets, e.g. planets orbiting quiet M-dwarfs or with a photochemical UV shield. If detected, PH$_3$ is a promising biosignature gas, as it has no known abiotic false positives on terrestrial planets that could generate the high fluxes required for detection. PH$_3$ also has 3 strong spectral features such that in any atmosphere scenario 1 of the 3 will be unique compared to other dominant spectroscopic molecules. PH$_3$'s weakness as a biosignature gas is its high reactivity, requiring high outgassing for detectability. We calculate that 10s of hours of JWST time are required for a potential detection of PH$_3$. Yet because PH$_3$ is spectrally active in the same wavelength regions as other atmospherically important molecules (e.g., H$_2$O and CH$_4$), searches for PH$_3$ can be carried out at no additional observational cost to searches for other molecules relevant to exoplanet habitability., Comment: Accepted to Astrobiology. Expected publication info: Volume 20, Issue 2

A key challenge in origins-of-life studies is estimating the abundances of species relevant to the chemical pathways proposed to have contributed to the emergence of life on early Earth. Dissolved nitrogen oxide anions (NO$_{X}^{-}$), in particular nitrate (NO$_{3}^{-}$) and nitrite (NO$_{2}^{-}$), have been invoked in diverse origins-of-life chemistry, from the oligomerization of RNA to the emergence of protometabolism. Recent work has calculated the supply of NO$_{X}^{-}$ from the prebiotic atmosphere to the ocean, and reported steady-state [NO$_{X}^{-}$] to be high across all plausible parameter space. These findings rest on the assumption that NO$_{X}^{-}$ is stable in natural waters unless processed at a hydrothermal vent. Here, we show that NO$_{X}^{-}$ is unstable in the reducing environment of early Earth. Sinks due to UV photolysis and reactions with reduced iron (Fe$^{2+}$) suppress [NO$_{X}^{-}$] by several orders of magnitude relative to past predictions. For pH$=6.5-8$ and $T=0-50^\circ$C, we find that it is most probable that NO$_{X}^{-}$]$<1~\mu$M in the prebiotic ocean. On the other hand, prebiotic ponds with favorable drainage characteristics may have sustained [NO$_{X}^{-}$]$\geq 1~\mu$M. As on modern Earth, most NO$_{X}^{-}$ on prebiotic Earth should have been present as NO$_{3}^{-}$, due to its much greater stability. These findings inform the kind of prebiotic chemistries that would have been possible on early Earth. We discuss the implications for proposed prebiotic chemistries, and highlight the need for further studies of NO$_{X}^{-}$ kinetics to reduce the considerable uncertainties in predicting [NO$_{X}^{-}$] on early Earth., Comment: In review for publication at Geochemistry, Geophysics, and Geosystems (G-cubed). Comments, questions, and criticism solicited; please contact corresponding author at sukrit@mit.edu. SI at: https://web-cert.mit.edu/sukrit/Public/nox_si.pdf. GitHub at: https://github.com/sukritranjan/nox

We perform a study of stellar flares for the 24,809 stars observed with 2 minute cadence during the first two months of the TESS mission. Flares may erode exoplanets' atmospheres and impact their habitability, but might also trigger the genesis of life around small stars. TESS provides a new sample of bright dwarf stars in our galactic neighborhood, collecting data for thousands of M-dwarfs that might host habitable exoplanets. Here, we use an automated search for flares accompanied by visual inspection. Then, our public allesfitter code robustly selects the appropriate model for potentially complex flares via Bayesian evidence. We identify 1228 flaring stars, 673 of which are M-dwarfs. Among 8695 flares in total, the largest superflare increased the stellar brightness by a factor of 16.1. Bolometric flare energies range from 10^31.0 to 10^36.9 erg, with a median of 10^33.1 erg. Furthermore, we study the flare rate and energy as a function of stellar type and rotation period. We solidify past findings that fast rotating M-dwarfs are the most likely to flare, and that their flare amplitude is independent of the rotation period. Finally, we link our results to criteria for prebiotic chemistry, atmospheric loss through coronal mass ejections, and ozone sterilization. Four of our flaring M dwarfs host exoplanet candidates alerted on by TESS, for which we discuss how these effects can impact life. With upcoming TESS data releases, our flare analysis can be expanded to almost all bright small stars, aiding in defining criteria for exoplanet habitability., Comment: Published in The Astronomical Journal, 159, 60. 21 pages, 11 figures, 2 tables. This is the authors' version of the manuscript

Highly volcanic exoplanets, which can be variously characterized as 'lava worlds', 'magma ocean worlds', or 'super-Ios' are high priority targets for investigation. The term 'lava world' may refer to any planet with extensive surface lava lakes, while the term 'magma ocean world' refers to planets with global or hemispherical magma oceans at their surface. 'Highly volcanic planets', including super-Ios, may simply have large, or large numbers of, active explosive or extrusive volcanoes of any form. They are plausibly highly diverse, with magmatic processes across a wide range of compositions, temperatures, activity rates, volcanic eruption styles, and background gravitational force magnitudes. Worlds in all these classes are likely to be the most characterizable rocky exoplanets in the near future due to observational advantages that stem from their preferential occurrence in short orbital periods and their bright day-side flux in the infrared. Transit techniques should enable a level of characterization of these worlds analogous to hot Jupiters. Understanding processes on highly volcanic worlds is critical to interpret imminent observations. The physical states of these worlds are likely to inform not just geodynamic processes, but also planet formation, and phenomena crucial to habitability. Volcanic and magmatic activity uniquely allows chemical investigation of otherwise spectroscopically inaccessible interior compositions. These worlds will be vital to assess the degree to which planetary interior element abundances compare to their stellar hosts, and may also offer pathways to study both the very young Earth, and the very early form of many silicate planets where magma oceans and surface lava lakes are expected to be more prevalent. We suggest that highly volcanic worlds may become second only to habitable worlds in terms of both scientific and public long-term interest., Comment: A white paper submitted in response to the National Academy of Sciences 2018 Exoplanet Science Strategy solicitation, from the NASA Sellers Exoplanet Environments Collaboration (SEEC) of the Goddard Space Flight Center. 6 pages, 0 figures

A key challenge in origin-of-life studies is understanding the environmental conditions on early Earth under which abiogenesis occurred. While some constraints do exist (e.g., zircon evidence for surface liquid water), relatively few constraints exist on the abundances of trace chemical species, which are relevant to assessing the plausibility and guiding the development of postulated prebiotic chemical pathways which depend on these species. In this work, we combine literature photochemistry models with simple equilibrium chemistry calculations to place constraints on the plausible range of concentrations of sulfidic anions (HS$^-$, HSO$_3^{-}$, SO$_3^{2-}$) available in surficial aquatic reservoirs on early Earth due to outgassing of SO$_2$ and H$_2$S and their dissolution into small shallow surface water reservoirs like lakes. We find that this mechanism could have supplied prebiotically relevant levels of SO$_2$-derived anions, but not H$_2$S-derived anions. Radiative transfer modelling suggests UV light would have remained abundant on the planet surface for all but the largest volcanic explosions. We apply our results to the case study of the proposed prebiotic reaction network of Patel et al. (2015), and discuss the implications for improving its prebiotic plausibility. In general, epochs of moderately high volcanism could have been especially conducive to cyanosulfidic prebiotic chemistry. Our work can be similarly applied to assess and improve the prebiotic plausibility of other postulated surficial prebiotic chemistries that are sensitive to sulfidic anions, and our methods adapted to study other atmospherically-derived trace species., Comment: Accepted to Astrobiology; comments welcome

Potentially-habitable planets orbiting M-dwarfs are of intense astrobiological interest because they are the only rocky worlds accessible to biosignature search over the next 10+ years due to a confluence of observational effects. Simultaneously, recent experimental and theoretical work suggests that UV light may have played a key role in the origin of life on Earth, and especially the origin of RNA. Characterizing the UV environment on M-dwarfs planets is important to understanding whether life as we know it could emerge on such worlds. In this work, we couple radiative transfer models to observed M-dwarf spectra to determine the UV environment on prebiotic Earth-analog planets orbiting M-dwarfs. We calculate dose rates to quantify the impact of different host stars on prebiotically-important photoprocesses. We find that M-dwarf planets have access to 100-1000 times less bioactive UV fluence than the young Earth. It is unclear whether UV-sensitive prebiotic chemistry that may have been important to abiogenesis, such as the only known prebiotically plausible pathways for pyrimidine ribonucleotide synthesis, could function on M-dwarf planets. This uncertainty affects objects like the recently-discovered habitable-zone planets orbiting Proxima Centauri, TRAPPIST-1, and LHS 1140. Laboratory studies of the sensitivity of putative prebiotic pathways to irradiation level are required to resolve this uncertainty. If steady-state M-dwarf UV output is insufficient to power these pathways, transient elevated UV irradiation due to flares may suffice; laboratory studies can constrain this possibility as well., Comment: 18 pages; 6 figures; published in ApJ

Recent findings suggest Mars may have been a clement environment for the emergence of life, and may even have compared favorably to Earth in this regard. These findings have revived interest in the hypothesis that prebiotically important molecules or even nascent life may have formed on Mars and been transferred to Earth. UV light plays a key role in prebiotic chemistry. Characterizing the early Martian surface UV environment is key to understanding how Mars compares to Earth as a venue for prebiotic chemistry. Here, we present two-stream multi-layer calculations of the UV surface radiance on Mars at 3.9 Ga, to constrain the surface UV environment as a function of atmospheric state. We explore a wide range of atmospheric pressures, temperatures and compositions, corresponding to the diversity of Martian atmospheric states consistent with available constraints. We include the effects of clouds and dust. We calculate dose rates to quantify the effect of different atmospheric states on UV-sensitive prebiotic chemistry. We find that for normative clear-sky CO2-H2O atmospheres, the UV environment on young Mars is comparable to young Earth. This similarity is robust to moderate cloud cover: thick clouds ($\tau$>100) are required to significantly affect the Martian UV environment, because cloud absorption is degenerate with atmospheric CO2. On the other hand, absorption from SO2, H2S, and dust is nondegenerate with CO2, meaning if they can build up to high levels, surface UV fluence will be suppressed. These absorbers have spectrally variable absorption, meaning that their presence affects prebiotic pathways in different ways. In particular, high SO2 environments may admit UV fluence that favors pathways conducive to abiogenesis over pathways unfavorable to it. However, better measurements of the spectral quantum yields of these pathways are required to evaluate this hypothesis definitively., Comment: In press at Astrobiology; minor errors fixed relative to v1,2

The UV environment is a key boundary condition for the origin of life. However, considerable uncertainty exists as to planetary conditions and hence surface UV at abiogenesis. Here, we present two-stream multi-layer clear-sky calculations of the UV surface radiance on Earth at 3.9 Ga to constrain the UV surface fluence as a function of albedo, solar zenith angle (SZA), and atmospheric composition. Variation in albedo and latitude (through SZA) can affect maximum photoreaction rates by a factor of >10.4; for the same atmosphere, photoreactions can proceed an order of magnitude faster at the equator of a snowball Earth than at the poles of a warmer world. Surface conditions are important considerations when computing prebiotic UV fluences. For climatically reasonable levels of CO2, fluence shortward of 189 nm is screened out, meaning that prebiotic chemistry is robustly shielded from variations in UV fluence due to solar flares or variability. Strong shielding from CO2 also means that the UV surface fluence is insensitive to plausible levels of CH4, O2, and O3. At scattering wavelengths, UV fluence drops off comparatively slowly with increasing CO2 levels. However, if SO2 and/or H2S can build up to the 1-100 ppm level as hypothesized by some workers, then they can dramatically suppress surface fluence and hence prebiotic photoprocesses. H2O is a robust UV shield for <198 nm. This means that regardless of the levels of other atmospheric gases, fluence <198 nm is only available for cold, dry atmospheres, meaning sources with emission <198 nm (e.g. ArF eximer lasers) can only be used in simulations of cold environments with low abundance of volcanogenic gases. On the other hand, fluence at 254 nm is unshielded by H2O and is available across a broad range of CO2 columns, meaning that mercury lamps are suitable for initial studies regardless of the uncertainty in primordial H2O and CO2 levels., Comment: Accepted to Astrobiology. Preprint format; 3 tables, 29 figures, 95 pages)

Ultraviolet (UV) radiation is common to most planetary environments, and could play a key role in the chemistry of molecules relevant to abiogenesis (prebiotic chemistry). In this work, we explore the impact of UV light on prebiotic chemistry that might occur in liquid water on the surface of a planet with an atmosphere. We consider effects including atmospheric absorption, attenuation by water, and stellar variability to constrain the UV input as a function of wavelength. We conclude that the UV environment would be characterized by broadband input, and wavelengths below 204 nm and 168 nm would be shielded out by atmospheric CO2 and water, respectively. We compare this broadband prebiotic UV input to the narrowband UV sources (e.g. mercury lamps) often used in laboratory studies of prebiotic chemistry, and explore the implications for the conclusions drawn from these experiments. We consider as case studies the ribonucleotide synthesis pathway of Powner et al (2009) and the sugar synthesis pathway of Ritson et al (2012). Irradiation by narrowband UV light from a mercury lamp formed an integral component of these studies: we quantitatively explore the impact of more realistic UV input on the conclusions that can be drawn from these experiments. Finally, we explore the constraints solar UV input places on the buildup of prebiotically important feedstock gasses like CH4 and HCN. Our results demonstrate the importance of characterizing the wavelength dependence (action spectra) of prebiotic synthesis pathways to determine how pathways derived under laboratory irradiation conditions will function under planetary prebiotic conditions. Keywords: Laboratory Investigations; Origin of Life; Planetary Environments; UV Radiation; RNA World, Comment: Accepted to Astrobiology. 8 figures, 2 tables

We probe the structure and composition of the atmospheres of 5 hot Jupiter exoplanets using the Hubble Space Telescope Wide Field Camera 3 (WFC3) instrument. We use the G141 grism (1.1-1.7 $\mu$m) to study TrES-2b, TrES-4b, and CoRoT-1b in transit, TrES-3b in secondary eclipse, and WASP-4b in both. This wavelength region includes a predicted absorption feature from water at 1.4 $\mu$m, which we expect to be nondegenerate with the other molecules that are likely to be abundant for hydrocarbon-poor (e.g. solar composition) hot Jupiter atmospheres. We divide our wavelength regions into 10 bins. For each bin we produce a spectrophotometric light curve spanning the time of transit and/or eclipse. We correct these light curves for instrumental systematics without reference to an instrument model. For our transmission spectra, our mean $1-\sigma$ precision per bin corresponds to variations of 2.1, 2.8, and 3.0 atmospheric scale heights for TrES-2b, TrES-4b, and CoRoT-1b, respectively. We find featureless spectra for these three planets. We are unable to extract a robust transmission spectrum for WASP-4b. For our dayside emission spectra, our mean $1-\sigma$ precision per bin corresponds to a planet-to-star flux ratio of $1.5\times10^{-4}$ and $2.1\times10^{-4}$ for WASP-4b and TrES-3b, respectively. We combine these estimates with previous broadband measurements and conclude that for both planets isothermal atmospheres are disfavored. We find no signs of features due to water. We confirm that WFC3 is suitable for studies of transiting exoplanets, but in staring mode multi-visit campaigns are necessary to place strong constraints on water abundance., Comment: Accepted to ApJ

We have used Hubble/WFC3 and the G141 grism to measure the secondary eclipse of the transiting very hot Jupiter CoRoT-2b in the 1.1-1.7$\mu$m spectral region. We find an eclipse depth averaged over this band equal to $395^{+69}_{-45}$ parts per million, equivalent to a blackbody temperature of $1788\pm18$K. We study and characterize several WFC3 instrumental effects, especially the "hook" phenomenon described by Deming et al. (2013). We use data from several transiting exoplanet systems to find a quantitative relation between the amplitude of the hook and the exposure level of a given pixel. Although the uncertainties in this relation are too large to allow us to develop an empirical correction for our data, our study provides a useful guide for optimizing exposure levels in future WFC3 observations. We derive the planet's spectrum using a differential method. The planet-to-star contrast increases to longer wavelength within the WFC3 bandpass, but without water absorption or emission to a $3\sigma$ limit of 85 ppm. The slope of the WFC3 spectrum is significantly less than the slope of the best-fit blackbody. We compare all existing eclipse data for this planet to a blackbody spectrum, and to spectra from both solar abundance and carbon-rich (C/O=1) models. A blackbody spectrum is an acceptable fit to the full dataset. Extra continuous opacity due to clouds or haze, and flattened temperature profiles, are strong candidates to produce quasi-blackbody spectra, and to account for the amplitude of the optical eclipses. Our results show ambiguous evidence for a temperature inversion in this planet., Comment: 18 pages, 14 figures. Accepted for publication in ApJ on 1/16/2014

Exoplanetary transmission spectroscopy in the near-infrared using Hubble/NICMOS is currently ambiguous because different observational groups claim different results from the same data, depending on their analysis methodologies. Spatial scanning with Hubble/WFC3 provides an opportunity to resolve this ambiguity. We here report WFC3 spectroscopy of the giant planets HD209458b and XO-1b in transit, using spatial scanning mode for maximum photon-collecting efficiency. We introduce an analysis technique that derives the exoplanetary transmission spectrum without the necessity of explicitly decorrelating instrumental effects, and achieves nearly photon-limited precision even at the high flux levels collected in spatial scan mode. Our errors are within 6-percent (XO-1) and 26-percent (HD209458b) of the photon-limit at a spectral resolving power of 70, and are better than 0.01-percent per spectral channel. Both planets exhibit water absorption of approximately 200 ppm at the water peak near 1.38 microns. Our result for XO-1b contradicts the much larger absorption derived from NICMOS spectroscopy. The weak water absorption we measure for HD209458b is reminiscent of the weakness of sodium absorption in the first transmission spectroscopy of an exoplanet atmosphere by Charbonneau et al. (2002). Model atmospheres having uniformly-distributed extra opacity of 0.012 cm^2 per gram account approximately for both our water measurement and the sodium absorption in this planet. Our results for HD209458b support the picture advocated by Pont et al. (2013) in which weak molecular absorptions are superposed on a transmission spectrum that is dominated by continuous opacity due to haze and/or dust. However, the extra opacity needed for HD209458b is grayer than for HD189733b, with a weaker Rayleigh component., Comment: new figures, one new table, minor text revisions, accepted for ApJ