Chemical conditions on Hycean worlds.

Traditionally, the search for life on exoplanets has been predominantly focused on rocky exoplanets. The recently proposed Hycean worlds have the potential to significantly expand and accelerate the search for life elsewhere. Hycean worlds are a class of habitable sub-Neptunes with planet-wide oceans and H2-rich atmospheres. Their broad range of possible sizes and temperatures lead to a wide habitable zone and high potential for discovery and atmospheric characterization using transit spectroscopy. Over a dozen candidate Hycean planets are already known to be transiting nearby M dwarfs, making them promising targets for atmospheric characterization with the James Webb Space Telescope (JWST). In this work, we investigate possible chemical conditions on a canonical Hycean world, focusing on (a) the present and primordial molecular composition of the atmosphere, and (b) the inventory of bioessential elements for the origin and sustenance of life in the ocean. Based on photochemical and kinetic modeling for a range of conditions, we discuss the possible chemical evolution and observable present-day composition of its atmosphere. In particular, for reduced primordial conditions the early atmospheric evolution passes through a phase that is rich in organic molecules that could provide important feedstock for prebiotic chemistry. We investigate avenues for delivering bioessential metals to the ocean, considering the challenging lack of weathering from a rocky surface and the ocean separated from the rocky core by a thick icy mantle. Based on ocean depths from internal structure modelling and elemental estimates for the early Earth's oceans, we estimate the requirements for bioessential metals in such a planet. We find that the requirements can be met for plausible assumptions about impact history and atmospheric sedimentation, and supplemented by other steady state sources. We discuss the observational prospects for atmospheric characterisation of Hycean worlds with JWST and future directions of this new paradigm in the search for life on exoplanets.

Detection of titanium oxide in the atmosphere of a hot Jupiter.

As an exoplanet transits its host star, some of the light from the star is absorbed by the atoms and molecules in the planet's atmosphere, causing the planet to seem bigger; plotting the planet's observed size as a function of the wavelength of the light produces a transmission spectrum. Measuring the tiny variations in the transmission spectrum, together with atmospheric modelling, then gives clues to the properties of the exoplanet's atmosphere. Chemical species composed of light elements-such as hydrogen, oxygen, carbon, sodium and potassium-have in this way been detected in the atmospheres of several hot giant exoplanets, but molecules composed of heavier elements have thus far proved elusive. Nonetheless, it has been predicted that metal oxides such as titanium oxide (TiO) and vanadium oxide occur in the observable regions of the very hottest exoplanetary atmospheres, causing thermal inversions on the dayside. Here we report the detection of TiO in the atmosphere of the hot-Jupiter planet WASP-19b. Our combined spectrum, with its wide spectral coverage, reveals the presence of TiO (to a confidence level of 7.7σ), a strongly scattering haze (7.4σ) and sodium (3.4σ), and confirms the presence of water (7.9σ) in the atmosphere.

A map of the large day-night temperature gradient of a super-Earth exoplanet.

Over the past decade, observations of giant exoplanets (Jupiter-size) have provided key insights into their atmospheres, but the properties of lower-mass exoplanets (sub-Neptune) remain largely unconstrained because of the challenges of observing small planets. Numerous efforts to observe the spectra of super-Earths--exoplanets with masses of one to ten times that of Earth--have so far revealed only featureless spectra. Here we report a longitudinal thermal brightness map of the nearby transiting super-Earth 55 Cancri e (refs 4, 5) revealing highly asymmetric dayside thermal emission and a strong day-night temperature contrast. Dedicated space-based monitoring of the planet in the infrared revealed a modulation of the thermal flux as 55 Cancri e revolves around its star in a tidally locked configuration. These observations reveal a hot spot that is located 41 ± 12 degrees east of the substellar point (the point at which incident light from the star is perpendicular to the surface of the planet). From the orbital phase curve, we also constrain the nightside brightness temperature of the planet to 1,380 ± 400 kelvin and the temperature of the warmest hemisphere (centred on the hot spot) to be about 1,300 kelvin hotter (2,700 ± 270 kelvin) at a wavelength of 4.5 micrometres, which indicates inefficient heat redistribution from the dayside to the nightside. Our observations are consistent with either an optically thick atmosphere with heat recirculation confined to the planetary dayside, or a planet devoid of atmosphere with low-viscosity magma flows at the surface.

Water vapour absorption in the clear atmosphere of a Neptune-sized exoplanet.

Transmission spectroscopy has so far detected atomic and molecular absorption in Jupiter-sized exoplanets, but intense efforts to measure molecular absorption in the atmospheres of smaller (Neptune-sized) planets during transits have revealed only featureless spectra. From this it was concluded that the majority of small, warm planets evolve to sustain atmospheres with high mean molecular weights (little hydrogen), opaque clouds or scattering hazes, reducing our ability to observe the composition of these atmospheres. Here we report observations of the transmission spectrum of the exoplanet HAT-P-11b (which has a radius about four times that of Earth) from the optical wavelength range to the infrared. We detected water vapour absorption at a wavelength of 1.4 micrometres. The amplitude of the water absorption (approximately 250 parts per million) indicates that the planetary atmosphere is predominantly clear down to an altitude corresponding to about 1 millibar, and sufficiently rich in hydrogen to have a large scale height (over which the atmospheric pressure varies by a factor of e). The spectrum is indicative of a planetary atmosphere in which the abundance of heavy elements is no greater than about 700 times the solar value. This is in good agreement with the core-accretion theory of planet formation, in which a gas giant planet acquires its atmosphere by accreting hydrogen-rich gas directly from the protoplanetary nebula onto a large rocky or icy core.

A high C/O ratio and weak thermal inversion in the atmosphere of exoplanet WASP-12b.

The carbon-to-oxygen ratio (C/O) in a planet provides critical information about its primordial origins and subsequent evolution. A primordial C/O greater than 0.8 causes a carbide-dominated interior, as opposed to the silicate-dominated composition found on Earth; the atmosphere can also differ from those in the Solar System. The solar C/O is 0.54 (ref. 3). Here we report an analysis of dayside multi-wavelength photometry of the transiting hot-Jupiter WASP-12b (ref. 6) that reveals C/O ≥ 1 in its atmosphere. The atmosphere is abundant in CO. It is depleted in water vapour and enhanced in methane, each by more than two orders of magnitude compared to a solar-abundance chemical-equilibrium model at the expected temperatures. We also find that the extremely irradiated atmosphere (T > 2,500 K) of WASP-12b lacks a prominent thermal inversion (or stratosphere) and has very efficient day-night energy circulation. The absence of a strong thermal inversion is in stark contrast to theoretical predictions for the most highly irradiated hot-Jupiter atmospheres.

Possible thermochemical disequilibrium in the atmosphere of the exoplanet GJ 436b.

The nearby extrasolar planet GJ 436b-which has been labelled as a 'hot Neptune'-reveals itself by the dimming of light as it crosses in front of and behind its parent star as seen from Earth. Respectively known as the primary transit and secondary eclipse, the former constrains the planet's radius and mass, and the latter constrains the planet's temperature and, with measurements at multiple wavelengths, its atmospheric composition. Previous work using transmission spectroscopy failed to detect the 1.4-mum water vapour band, leaving the planet's atmospheric composition poorly constrained. Here we report the detection of planetary thermal emission from the dayside of GJ 436b at multiple infrared wavelengths during the secondary eclipse. The best-fit compositional models contain a high CO abundance and a substantial methane (CH(4)) deficiency relative to thermochemical equilibrium models for the predicted hydrogen-dominated atmosphere. Moreover, we report the presence of some H(2)O and traces of CO(2). Because CH(4) is expected to be the dominant carbon-bearing species, disequilibrium processes such as vertical mixing and polymerization of methane into substances such as ethylene may be required to explain the hot Neptune's small CH(4)-to-CO ratio, which is at least 10(5) times smaller than predicted.

Exoplanetary Atmospheres-Chemistry, Formation Conditions, and Habitability.

Characterizing the atmospheres of extrasolar planets is the new frontier in exoplanetary science. The last two decades of exoplanet discoveries have revealed that exoplanets are very common and extremely diverse in their orbital and bulk properties. We now enter a new era as we begin to investigate the chemical diversity of exoplanets, their atmospheric and interior processes, and their formation conditions. Recent developments in the field have led to unprecedented advancements in our understanding of atmospheric chemistry of exoplanets and the implications for their formation conditions. We review these developments in the present work. We review in detail the theory of atmospheric chemistry in all classes of exoplanets discovered to date, from highly irradiated gas giants, ice giants, and super-Earths, to directly imaged giant planets at large orbital separations. We then review the observational detections of chemical species in exoplanetary atmospheres of these various types using different methods, including transit spectroscopy, Doppler spectroscopy, and direct imaging. In addition to chemical detections, we discuss the advances in determining chemical abundances in these atmospheres and how such abundances are being used to constrain exoplanetary formation conditions and migration mechanisms. Finally, we review recent theoretical work on the atmospheres of habitable exoplanets, followed by a discussion of future outlook of the field.

Exoplanet atmosphere. Thermal structure of an exoplanet atmosphere from phase-resolved emission spectroscopy.

Exoplanets that orbit close to their host stars are much more highly irradiated than their solar system counterparts. Understanding the thermal structures and appearances of these planets requires investigating how their atmospheres respond to such extreme stellar forcing. We present spectroscopic thermal emission measurements as a function of orbital phase ("phase-curve observations") for the highly irradiated exoplanet WASP-43b spanning three full planet rotations using the Hubble Space Telescope. With these data, we construct a map of the planet's atmospheric thermal structure, from which we find large day-night temperature variations at all measured altitudes and a monotonically decreasing temperature with pressure at all longitudes. We also derive a Bond albedo of 0.18(-0.12)(+0.07) and an altitude dependence in the hot-spot offset relative to the substellar point.

Astrobiological stoichiometry.

Chemical composition affects virtually all aspects of astrobiology, from stellar astrophysics to molecular biology. We present a synopsis of the research results presented at the "Stellar Stoichiometry" Workshop Without Walls hosted at Arizona State University April 11-12, 2013, under the auspices of the NASA Astrobiology Institute. The results focus on the measurement of chemical abundances and the effects of composition on processes from stellar to planetary scales. Of particular interest were the scientific connections between processes in these normally disparate fields. Measuring the abundances of elements in stars and giant and terrestrial planets poses substantial difficulties in technique and interpretation. One of the motivations for this conference was the fact that determinations of the abundance of a given element in a single star by different groups can differ by more than their quoted errors. The problems affecting the reliability of abundance estimations and their inherent limitations are discussed. When these problems are taken into consideration, self-consistent surveys of stellar abundances show that there is still substantial variation (factors of ∼ 2) in the ratios of common elements (e.g., C, O, Na, Al, Mg, Si, Ca) important in rock-forming minerals, atmospheres, and biology. We consider how abundance variations arise through injection of supernova nucleosynthesis products into star-forming material and through photoevaporation of protoplanetary disks. The effects of composition on stellar evolution are substantial, and coupled with planetary atmosphere models can result in predicted habitable zone extents that vary by many tens of percent. Variations in the bulk composition of planets can affect rates of radiogenic heating and substantially change the mineralogy of planetary interiors, affecting properties such as convection and energy transport.