H2-dominated Atmospheres Research Articles

HCN Production in Titan’s Atmosphere: Coupling Quantum Chemistry and Disequilibrium Atmospheric Modeling

Abstract Hydrogen cyanide (HCN) is a critical reactive source of nitrogen for building key biomolecules relevant for the origin of life. Still, many HCN reactions remain uncharacterized by experiments and theory, and the complete picture of HCN production in planetary atmospheres is not fully understood. To improve this situation, we develop a novel technique making use of computational quantum chemistry, experimental data, and atmospheric numerical simulations. First, we use quantum chemistry simulations to explore the entire field of possible reactions for a list of primary species in N2-, CH4-, and H2-dominated atmospheres. In this process, we discover 33 new reactions with no previously known rate coefficients. From here, we develop a consistent reduced atmospheric hybrid chemical network (CRAHCN) containing experimental values when available and our calculated rate coefficients otherwise. Next, we couple CRAHCN to a 1D chemical kinetic model (ChemKM) to compute the HCN abundance as a function of atmospheric depth on Titan. Our simulated atmospheric HCN profile agrees very well with the Cassini observations. CRAHCN contains 104 reactions; however, nearly all of the simulated atmospheric HCN profile can be obtained using a scaled-down network of only 19 dominant reactions. From here, we form a complete picture of HCN chemistry in Titan’s atmosphere, from the dissociation of the main atmospheric species, down to the direct production of HCN along four major channels. One of these channels was first discovered and characterized in Pearce et al. and this work.

CRAHCN-O: A Consistent Reduced Atmospheric Hybrid Chemical Network Oxygen Extension for Hydrogen Cyanide and Formaldehyde Chemistry in CO2-, N2-, H2O-, CH4-, and H2-Dominated Atmospheres.

Hydrogen cyanide (HCN) and formaldehyde (H2CO) are key precursors to biomolecules such as nucleobases and amino acids in planetary atmospheres. However, many reactions which produce and destroy these species in atmospheres containing CO2 and H2O are still missing from the literature. We use a quantum chemistry approach to find these missing reactions and calculate their rate coefficients using canonical variational transition state theory and Rice-Ramsperger-Kassel-Marcus/master equation theory at the BHandHLYP/aug-cc-pVDZ level of theory. We calculate the rate coefficients for 126 total reactions and validate our calculations by comparing with experimental data in the 39% of available cases. Our calculated rate coefficients are most frequently within a factor of 2 of experimental values and generally always within an order of magnitude of these values. We discover 45 previously unknown reactions and identify 6 from this list that are most likely to dominate H2CO and HCN production and destruction in planetary atmospheres. We highlight 1O + CH3 → H2CO + H as a new key source and H2CO + 1O → HCO + OH as a new key sink, for H2CO in upper planetary atmospheres. In this effort, we develop an oxygen extension to our consistent reduced atmospheric hybrid chemical network (CRAHCN-O), building off our previously developed network for HCN production in N2-, CH4-, and H2-dominated atmospheres (CRAHCN). This extension can be used to simulate both HCN and H2CO production in atmospheres dominated by any of CO2, N2, H2O, CH4, and H2.

Mineral cloud and hydrocarbon haze particles in the atmosphere of the hot Jupiter JWST target WASP-43b

Context. Having a short orbital period and being tidally locked makes WASP-43b an ideal candidate for the James Webb Space Telescope (JWST) phase curve measurements. Phase curve observations of an entire orbit will enable the mapping of the atmospheric structure across the planet, with different wavelengths of observation allowing different atmospheric depths to be seen. Aims. We provide insight into the details of the clouds that may form on WASP-43b and their impact on the remaining gas phase, in order to prepare the forthcoming interpretation of the JWST and follow-up data. Methods. We follow a hierarchical modelling strategy. We utilise 3D GCM results as input for a kinetic, non-equilibrium model for mineral cloud particles and for a kinetic model to study a photochemically-driven hydrocarbon haze component. Results. Mineral condensation seeds form throughout the atmosphere of WASP-43b. This is in stark contrast to the ultra-hot Jupiters, such as WASP-18b and HAT-P-7b. The dayside is not cloud free but it is loaded with few yet large mineral cloud particles in addition to hydrocarbon haze particles of a comparable abundance. Photochemically driven hydrocarbon haze appears on the dayside, but it does not contribute to the cloud formation on the nightside. The geometrical cloud extension differs across the globe due to the changing thermodynamic conditions. Day and night differ by 6000 km in pressure scale height. As reported for other planets, the C/O is not constant throughout the atmosphere and varies between 0.74 and 0.3. The mean molecular weight is approximately constant in a H2-dominated WASP-43b atmosphere because of the moderate day/night-temperature differences compared to the super-hot Jupiters. Conclusions. WASP-43b is expected to be fully covered in clouds which are not homogeneously distributed throughout the atmosphere. The dayside and the terminator clouds are a combination of mineral particles of locally varying size and composition as well as of hydrocarbon hazes. The optical depth of hydrocarbon hazes is considerably lower than that of mineral cloud particles such that a wavelength-dependent radius measurement of WASP-43b would be determined by the mineral cloud particles but not by hazes.

Exoplanet secondary atmosphere loss and revival

The next step on the path toward another Earth is to find atmospheres similar to those of Earth and Venus-high-molecular-weight (secondary) atmospheres-on rocky exoplanets. Many rocky exoplanets are born with thick (>10 kbar) H2-dominated atmospheres but subsequently lose their H2; this process has no known Solar System analog. We study the consequences of early loss of a thick H2 atmosphere for subsequent occurrence of a high-molecular-weight atmosphere using a simple model of atmosphere evolution (including atmosphere loss to space, magma ocean crystallization, and volcanic outgassing). We also calculate atmosphere survival for rocky worlds that start with no H2 Our results imply that most rocky exoplanets orbiting closer to their star than the habitable zone that were formed with thick H2-dominated atmospheres lack high-molecular-weight atmospheres today. During early magma ocean crystallization, high-molecular-weight species usually do not form long-lived high-molecular-weight atmospheres; instead, they are lost to space alongside H2 This early volatile depletion also makes it more difficult for later volcanic outgassing to revive the atmosphere. However, atmospheres should persist on worlds that start with abundant volatiles (for example, water worlds). Our results imply that in order to find high-molecular-weight atmospheres on warm exoplanets orbiting M-stars, we should target worlds that formed H2-poor, that have anomalously large radii, or that orbit less active stars.

Author Correction: Laboratory studies on the viability of life in H2-dominated exoplanet atmospheres

Author Correction: Laboratory studies on the viability of life in H2-dominated exoplanet atmospheres

Laboratory studies on the viability of life in H2-dominated exoplanet atmospheres

Theory and observation for the search for life on exoplanets via atmospheric "biosignature gases" is accelerating, motivated by the capabilities of the next generation of space- and ground-based telescopes. The most observationally accessible rocky planet atmospheres are those dominated by molecular hydrogen gas, because the low density of H$_2$-gas leads to an expansive atmosphere. The capability of life to withstand such exotic environments, however, has not been tested in this context. We demonstrate that single-celled microorganisms ($\textit{E. coli}$ and yeast) that normally do not inhabit H$_2$-dominated environments can survive and grow in a 100% H$_2$ atmosphere. We also describe the astonishing diversity of dozens of different gases produced by $\textit{E. coli}$, including many already proposed as potential biosignature gases (e.g., nitrous oxide, ammonia, methanethiol, dimethylsulfide, carbonyl sulfide, and isoprene). This work demonstrates the utility of lab experiments to better identify which kinds of alien environments can host some form of possibly detectable life.

Measurements and semi-empirical calculations of CO2 + CH4 and CO2 + H2 collision-induced absorption across a wide range of wavelengths and temperatures. Application for the prediction of early Mars surface temperature

Reducing atmospheres have recently emerged as a promising scenario to warm the surface of early Mars enough to drive the formation of valley networks and other ancient aqueous features that have been detected so far on the surface of Mars. Here we present a series of experiments and calculations to better constrain CO2 + CH4 and CO2 + H2 collision-induced absorptions (CIAs) as well as their effect on the prediction of early Mars surface temperature. First, we carried out a new set of experimental measurements (using the AILES line of the SOLEIL synchrotron) of both CO2 + CH4 and CO2 + H2 CIAs. These measurements confirm the previous results of Turbet et al. (2019), Icarus vol. 321, while significantly reducing the experimental uncertainties. Secondly, we fitted a semi-empirical model to these CIAs measurements, allowing us to compute the CO2 + CH4 and CO2 + H2 CIAs across a broad spectral domain (0–1500 cm−1) and for a wide range of temperatures (100–600 K). Last, we performed 1-D numerical radiative-convective climate calculations (using the LMD Generic Model) to compute the surface temperature expected on the surface of early Mars for several CO2, CH4 and H2 atmospheric contents, taking into account the radiative effect of these revised CIAs. These calculations demonstrate that thick CO2 + H2-dominated atmospheres remain a viable solution for warming the surface of Mars above the melting point of water, but not CO2 + CH4-dominated atmospheres. Our calculated CO2 + CH4 and CO2 + H2 CIA spectra and predicted early Mars surface temperatures are provided to the community for future uses.

Constraining the early evolution of Venus and Earth through atmospheric Ar, Ne isotope and bulk K/U ratios

The atmospheric noble gas isotope and elemental bulk ratios on Venus and Earth provide important information on their origin and evolution. If the protoplanets grew to a certain mass (i.e. > 0.5 MEarth), they could have captured H2-dominated primordial atmospheres by accreting gas from the circumstellar disk during the formation of the Solar System, which were then quickly lost by hydrodynamic escape after the disk dissipated. In such a case, the EUV-driven hydrodynamic flow of H atoms dragged heavier elements with it at different rates, leading to changes in their initial isotope ratios. For reproducing Earth and Venus present atmospheric 36Ar/38Ar, 20Ne/22Ne, 36Ar/22Ne, isotope and bulk K/U ratios we applied hydrodynamic upper atmosphere escape and Smooth Particle Hydrodynamics (SPH) impact models for the loss calculations of captured H2-dominated primordial atmospheres for various protoplanetary masses. We investigated a wide range of possible EUV evolution tracks of the young Sun and initial atmospheric compositions based on mixtures of captured nebula gas, outgassed and delivered material from ureilite, enstatite and carbonaceaous chondrites. Depending on the disk lifetime of ≈ 3–5 Myr (Bollard et al., 2017; Wang et al., 2017) and the composition of accreted material after disk dispersal, we find from the reproduction of the present atmospheric Ar, Ne, and bulk K/U ratios, that early Earth's evolution can be explained if proto-Earth had accreted masses between ≈ 0.53 − 0.58 MEarth by the time the nebula gas dissipated. If proto-Earth would have accreted a higher mass during the disk lifetime the present atmospheric Ar and Ne isotope ratios can not be reproduced with our model approach. For masses > 0.75 MEarth, Earth would have had a problem to get get rid of its primordial atmosphere. If proto-Earth accreted ≈ 0.53 − 0.58MEarth of enstatite-dominated material as suggested by Dauphas (2017) during the disk lifetime, it would have captured a tiny primordial atmosphere that was lost ≈ 3 Myr after the disk dissipated. In such a case we find that the present-day atmospheric Ar and Ne isotope ratios can be best reproduced if the post-nebula impactors contained ≈ 5% weakly depleted carbonaceous chondritic material and ≈ 95% enstatite chondrites that are strongly depleted in Ar, Ne and moderately volatile elements like potassium. If higher amounts of carbonaceous chondrites were involved in early Earth's accretion as recently suggested by Schiller et al. (2018), then the Earth's present atmospheric Ar and Ne ratios can only be reproduced if the involved carbonaceous chondritic post-nebula material was also highly depleted in these noble gases and/or had to be partially be delivered as long as the primordial atmosphere was yet escaping. As long as primordial atmospheres surround the growing protoplanets the abundance of their volatile elements is overwritten by their respective captured solar-like atmospheric abundances. Therefore the initial composition of the protoplanets at the disk dispersal time can not be identified by our method. For masses < 0.5 MEarth atmospheric escape cannot explain the present-day ratios, i.e. if Earth grew slower then these ratios have to be explained differently (Marty, 2012). If proto-Venus captured a primordial atmosphere it should have grown to masses of ≈ 0.85− 1.0 MVenus during the time until the disk dissipated and if early Venus accreted its main mass during the disk lifetime than the present atmospheric Ar and Ne isotope ratios and the observed K/U ratios on Venus surface can also be reproduced by the escape of a captured primordial atmosphere that is lost within ≤ 100 Myr, if the Sun was born as a weakly to moderately active young G star. New precise re-measurements of atmospheric noble gases are necessary by future Venus missions to better constrain the material that was involved in the planet's accretion history and possibly also the EUV activity evolution of the young Sun. In addition, measurements of other moderately volatile element and isotope ratios on the surface such as Rb/U, 64Zn/66Zn, and 39K/41K can give an insight on whether Venus accreted slow or fast, i.e. almost to its final mass within the disk lifetime.

Secondary Atmospheres on HD 219134 b and c

Abstract We analyze the interiors of HD 219134 b and c, which are among the coolest super-Earths detected thus far. Without using spectroscopic measurements, we aim at constraining if the possible atmospheres are hydrogen-rich or hydrogen-poor. In the first step, we employ a full probabilistic Bayesian inference analysis to rigorously quantify the degeneracy of interior parameters given the data of mass, radius, refractory element abundances, semimajor axes, and stellar irradiation. We obtain constraints on structure and composition for core, mantle, ice layer, and atmosphere. In the second step, we aim to draw conclusions on the nature of possible atmospheres by considering atmospheric escape. Specifically, we compare the actual possible atmospheres to a threshold thickness above which a primordial (H2-dominated) atmosphere can be retained against evaporation over the planet’s lifetime. The best-constrained parameters are the individual layer thicknesses. The maximum radius fraction of possible atmospheres are 0.18 and 0.13 R (radius), for planets b and c, respectively. These values are significantly smaller than the threshold thicknesses of primordial atmospheres: 0.28 and 0.19 R, respectively. Thus, the possible atmospheres of planets b and c are unlikely to be H2-dominated. However, whether possible volatile layers are made of gas or liquid/solid water cannot be uniquely determined. Our main conclusions are (1) the possible atmospheres for planets b and c are enriched and thus possibly secondary in nature, and (2) both planets may contain a gas layer, whereas the layer of HD 219134 b must be larger. HD 219134 c can be rocky.

Energies, transition probabilities, predissociation rates, and lifetimes of the , HD, and state

Transition probabilities of H2, HD, and D2 − electric dipole, − discrete-continuum magnetic dipole, and electric quadrupole transitions have been calculated using accurate energies and ro-vibrational wave functions obtained from precise ab initio potential energy curves. The predissociation rates of the () levels by direct and indirect spin–spin and spin–orbit coupling between − fine structure levels, have been also determined. The present investigation achieved good agreement with measured lifetimes of the fine structure levels without adjustment. A comparison of the calculated and observed lifetimes of metastable H2, HD, and D2 suggests that the − magnetic dipole and electric quadrupole transition moments underestimate the spontaneous emission rate of the metastable levels by ∼370 s−1. The measured and calculated lifetimes of H2, HD, and D2 fine structure levels are in very good agreement after the adjustment of 370 s−1 to the spontaneous decay rate of the − transition. The calculated energies, transition probabilities, and predissociation rates obtained in the present work, along with the state excitation function, are sufficient to determine the state emission cross section, the kinetic energy distribution of H(1s) atoms, and the energy deposition rate of the − excitation. In a previous investigation by Berg and Ottinger (1994 J. Chem. Phys. 100 8746), the authors were forced to insert a large scale factor into the predissociation rate in order to reconcile with measured lifetimes. Errors introduced in the approximations made in the previous investigations are discussed in the text. The H2 state has the second largest triplet state excitation cross section. Predissociation and spontaneous emission of the state plays an important role in the energy deposition of H2-dominated atmospheres.

HST HOT-JUPITER TRANSMISSION SPECTRAL SURVEY: CLEAR SKIES FOR COOL SATURN WASP-39b

ABSTRACT We present the Hubble Space Telescope (HST) Space Telescope Imaging Spectrograph (STIS) optical transmission spectroscopy of the cool Saturn-mass exoplanet WASP-39b from 0.29-1.025 μm, along with complementary transit observations from Spitzer IRAC at 3.6 and 4.5 μm. The low density and large atmospheric pressure scale height of WASP-39b make it particularly amenable to atmospheric characterization using this technique. We detect a Rayleigh scattering slope as well as sodium and potassium absorption features; this is the first exoplanet in which both alkali features are clearly detected with the extended wings predicted by cloud-free atmosphere models. The full transmission spectrum is well matched by a clear H2-dominated atmosphere, or one containing a weak contribution from haze, in good agreement with the preliminary reduction of these data presented in Sing et al. WASP-39b is predicted to have a pressure-temperature profile comparable to that of HD 189733b and WASP-6b, making it one of the coolest transiting gas giants observed in our HST STIS survey. Despite this similarity, WASP-39b appears to be largely cloud-free, while the transmission spectra of HD 189733b and WASP-6b both indicate the presence of high altitude clouds or hazes. These observations further emphasize the surprising diversity of cloudy and cloud-free gas giant planets in short-period orbits and the corresponding challenges associated with developing predictive cloud models for these atmospheres.

SPECTRA, EMISSION YIELDS, CROSS SECTIONS, AND KINETIC ENERGY DISTRIBUTIONS OF HYDROGEN ATOMS FROM H2 – EXCITATION BY ELECTRON IMPACT

ABSTRACT Electron-impact excitation of H2 triplet states plays an important role in the heating of outer planet upper thermospheres. The d 3 &Pgr; u ?> state is the third ungerade triplet state, and the d 3 &Pgr; u ?> – a 3 &Sgr; g &plus; ?> emission is the largest cascade channel for the a 3 &Sgr; g &plus; ?> state. Accurate energies of the d 3 &Pgr; u &minus; ?> (v, J) levels are calculated from an ab initio potential energy curve. Radiative lifetimes of the d 3 &Pgr; u ?> (v, J) levels are obtained by an accurate evaluation of the d 3 &Pgr; u ?> – a 3 &Sgr; g &plus; ?> transition probabilities. The emission yields are determined from experimental lifetimes and calculated radiative lifetimes and are further verified by comparing experimental and synthetic d 3 &Pgr; u ?> – a 3 &Sgr; g &plus; ?> spectra at 20 eV impact energy. Spectral analysis revealed that multipolar components beyond the dipolar term are required to model the X 1 &Sgr; g &plus; ?> – d 3 &Pgr; u ?> excitation, and significant cascade excitation occurs at the d 3 &Pgr; u ?> (v = 0,1) levels. Kinetic energy (E k ) distributions of H atoms produced via predissociation of the d 3 &Pgr; u ?> state and the d 3 &Pgr; u ?> − a 3 &Sgr; g &plus; ?> − b 3 &Sgr; u &plus; ?> cascade dissociative emission are obtained. Predissociation of the d 3 &Pgr; u ?> state produces H atoms with an average E k of 2.3 ± 0.4 eV/atom, while the E k distribution of the d 3 &Pgr; u ?> − a 3 &Sgr; g &plus; ?> − b 3 &Sgr; u &plus; ?> channel is similar to that of the X 1 &Sgr; g &plus; ?> – a 3 &Sgr; g &plus; ?> − b 3 &Sgr; u &plus; ?> channel and produces H(1s) atoms with an average E k of 1.15 ± 0.05 eV/atom. On average, each H2 excited to the d 3 &Pgr; u ?> state in an H2-dominated atmosphere deposits 3.3 ± 0.4 eV into the atmosphere, while each H2 directly excited to the a 3 &Sgr; g &plus; ?> state gives 2.2–2.3 eV to the atmosphere. The spectral distribution of the calculated a 3 &Sgr; g &plus; ?> – b 3 &Sgr; u &plus; ?> continuum emission due to the X 1 &Sgr; g &plus; ?> – d 3 &Pgr; u ?> excitation is significantly different from that of direct a 3 &Sgr; g &plus; ?> excitation.

Photosynthesis in hydrogen-dominated atmospheres.

The diversity of extrasolar planets discovered in the last decade shows that we should not be constrained to look for life in environments similar to early or present-day Earth. Super-Earth exoplanets are being discovered with increasing frequency, and some will be able to retain a stable, hydrogen-dominated atmosphere. We explore the possibilities for photosynthesis on a rocky planet with a thin H2-dominated atmosphere. If a rocky, H2-dominated planet harbors life, then that life is likely to convert atmospheric carbon into methane. Outgassing may also build an atmosphere in which methane is the principal carbon species. We describe the possible chemical routes for photosynthesis starting from methane and show that less energy and lower energy photons could drive CH4-based photosynthesis as compared with CO2-based photosynthesis. We find that a by-product biosignature gas is likely to be H2, which is not distinct from the hydrogen already present in the environment. Ammonia is a potential biosignature gas of hydrogenic photosynthesis that is unlikely to be generated abiologically. We suggest that the evolution of methane-based photosynthesis is at least as likely as the evolution of anoxygenic photosynthesis on Earth and may support the evolution of complex life.

PHOTOCHEMISTRY IN TERRESTRIAL EXOPLANET ATMOSPHERES. III. PHOTOCHEMISTRY AND THERMOCHEMISTRY IN THICK ATMOSPHERES ON SUPER EARTHS AND MINI NEPTUNES

Some super Earths and mini Neptunes will likely have thick atmospheres that are not H2-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H2-dominated atmospheres and non-H2-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO2 rather than CH4 or CO in a H2-depleted water-dominated thick atmosphere, and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to formation of unsaturated hydrocarbons (C2H2 and C2H4). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b like planets we find that (1) C2H2 features at 1.0 and 1.5 micron in transmission and C2H2 and C2H4 features at 9-14 micron in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.

HOW TO DISTINGUISH BETWEEN CLOUDY MINI-NEPTUNES AND WATER/VOLATILE-DOMINATED SUPER-EARTHS

One of the most profound questions about the newly discovered class of low-density super-Earths is whether these exoplanets are predominately H2-dominated mini-Neptunes or volatile-rich worlds with gas envelopes dominated by H2O, CO2, CO, CH4, or N2. Transit observations of the super-Earth GJ 1214b rule out a cloud-free H2-dominated atmosphere, but are not able to determine whether the lack of deep spectral features is due to high-altitude clouds or the presence of a high mean molecular mass atmosphere. Here, we demonstrate that one can unambiguously distinguish between cloudy mini-Neptunes and volatile-dominated worlds based on the differences in the wing steepness and relative depths of water absorption features in moderate-resolution NIR transmission spectra (R~100). In a numerical retrieval study, we show for GJ 1214b that an unambiguous distinction between a cloudy H2-dominated atmosphere and cloud-free H2 atmosphere will be possible if the uncertainties in the spectral transit depth measurements can be reduced by a factor of ~3 compared to the published HST WFC3 and VLT transit observations. We argue that the required precision for the distinction may be achievable with currently available instrumentation by stacking 10-15 transit observations. We provide a scaling law that scales our quantitative results to other transiting super-Earths and Neptunes such as HD 97658b, 55 Cnc e, and GJ 436b. The analysis is performed using an improved version of our Bayesian atmospheric retrieval framework. The new framework not only constrains the gas composition and cloud/haze parameters, but also determines our confidence in having detected molecules and cloud/haze species through Bayesian model comparison. Using the Bayesian tool, we demonstrate quantitatively that the subtle transit depth variation in the Berta et al. (2012) data is not sufficient to claim the detection of water absorption.

BIOSIGNATURE GASES IN H2-DOMINATED ATMOSPHERES ON ROCKY EXOPLANETS

(Abridged) Super Earth exoplanets are being discovered with increasing frequency and some will be able to retain stable H2-dominated atmospheres. We study biosignature gases on exoplanets with thin H2 atmospheres and habitable surface temperatures, by using a model atmosphere with photochemistry, and biomass estimate framework for evaluating the plausibilty of a range of biosignature gas candidates. We find that photochemically produced H atoms are the most abundant reactive species in H2 atmospheres. In atmospheres with high CO2 levels, atomic O is the major destructive species for some molecules. In sun-Earth-like UV radiation environments, H (and in some cases O) will rapidly destroy nearly all biosignature gases of interest. The lower UV fluxes from UV quiet M stars would produce a lower concentration of H (or O) for the same scenario, enabling some biosignature gases to accumulate. The favorability of low-UV radiation environments to in an H2 atmosphere is closely analogous to the case of oxidized atmospheres, where photochemically produced OH is the major destructive species. Most potential biosignature gases, such as DMS and CH3Cl are therefore more favorable in low UV, as compared to solar-like UV, environments. A few promising biosignature gas candidates, including NH3 and N2O, are favorable even in solar-like UV environments, as these gases are destroyed directly by photolysis and not by H (or O). A more subtle finding is that most gases produced by life that are fully hydrogenated forms of an element, such as CH4, H2S, are not effective signs of life in an H2-rich atmosphere, because the dominant atmospheric chemistry will generate such gases abiologically, through photochemistry or geochemistry. Suitable biosignature gases in H2-rich atmospheres for super Earth exoplanets transiting M stars could potentially be detected in transmission spectra with the JWST.

COMPOSITIONAL DIVERSITY IN THE ATMOSPHERES OF HOT NEPTUNES, WITH APPLICATION TO GJ 436b.

Neptune-sized extrasolar planets that orbit relatively close to their host stars - often called "hot Neptunes" - are common within the known population of exoplanets and planetary candidates. Similar to our own Uranus and Neptune, inefficient accretion of nebular gas is expected produce hot Neptunes whose masses are dominated by elements heavier than hydrogen and helium. At high atmospheric metallicities of 10-10,000× solar, hot Neptunes will exhibit an interesting continuum of atmospheric compositions, ranging from more Neptune-like, H2-dominated atmospheres to more Venus-like, CO2-dominated atmospheres. We explore the predicted equilibrium and disequilibrium chemistry of generic hot Neptunes and find that the atmospheric composition varies strongly as a function of temperature and bulk atmospheric properties such as metallicity and the C/O ratio. Relatively exotic H2O, CO, CO2, and even O2-dominated atmospheres are possible for hot Neptunes. We apply our models to the case of GJ 436b, where we find that a CO-rich, CH4-poor atmosphere can be a natural consequence of a very high atmospheric metallicity. From comparisons of our results with Spitzer eclipse data for GJ 436b, we conclude that although the spectral fit from the high-metallicity forward models is not quite as good as the best fit obtained from pure retrieval methods, the atmospheric composition predicted by these forward models is more physically and chemically plausible in terms of the relative abundance of major constituents. High-metallicity atmospheres (orders of magnitude in excess of solar) should therefore be considered as a possibility for GJ 436b and other hot Neptunes.

PHOTOCHEMISTRY IN TERRESTRIAL EXOPLANET ATMOSPHERES. II. H2S AND SO2PHOTOCHEMISTRY IN ANOXIC ATMOSPHERES

Sulfur gases are common components in the volcanic and biological emission on Earth, and are expected to be important input gases for atmospheres on terrestrial exoplanets. We study the atmospheric composition and the spectra of terrestrial exoplanets with sulfur compounds (i.e., H2S and SO2) emitted from their surfaces. We use a comprehensive one-dimensional photochemistry model and radiative transfer model to investigate the sulfur chemistry in atmospheres ranging from reducing to oxidizing. The most important finding is that both H2S and SO2 are chemically short-lived in virtually all types of atmospheres on terrestrial exoplanets, based on models of H2, N2, and CO2 atmospheres. This implies that direct detection of surface sulfur emission is unlikely, as their surface emission rates need to be extremely high (>1000 times Earth's volcanic sulfur emission) for these gases to build up to a detectable level. We also find that sulfur compounds emitted from the surface lead to photochemical formation of elemental sulfur and sulfuric acid in the atmosphere, which would condense to form aerosols if saturated. For terrestrial exoplanets in the habitable zone of Sun-like stars or M stars, Earth-like sulfur emission rates result in optically thick haze composed of elemental sulfur in reducing H2-dominated atmospheres for a wide range of particle diameters (0.1-1 micron), which is assumed as a free parameter in our simulations. In oxidized atmospheres composed of N2 and CO2, optically thick haze, composed of elemental sulfur aerosols (S8) or sulfuric acid aerosols (H2SO4), will form if the surface sulfur emission is 2 orders of magnitude more than the volcanic sulfur emission of Earth. Although direct detection of H2S and SO2 by their spectral features is unlikely, their emission might be inferred by observing aerosol-related features in reflected light with future generation space telescopes.

Potential atmospheric composition of smaller bodies in the solar system and some aspects of planetary evolution

A simple relationship indicating the maximum potential atmospheric surface density for a planetary body with a given radius, density, temperature structure, and atmospheric composition is developed. This result in conjunction with calculated exospheric temperatures for Mercury, Pluto, Triton, Titan, and the Galilean satellites of Jupiter permits an assessment of their ability to retain an appreciable atmosphere dominated by a particular constituent. These techniques are extended to the area of planetary evolution to (1) determine the stability of Jupiter at various locations in the solar system and (2) determine the minimum Jovian planetesimal radius capable of retaining a H2-dominated atmosphere under various solar conditions. The implications of these results are discussed.