Atmospheric chemical disequilibrium has been proposed as a method for detecting extraterrestrial biospheres from exoplanet observations. Chemical disequilibrium is potentially a generalized biosignature since it makes no assumptions about particular biogenic gases or metabolisms. Here, we present the first rigorous calculations of the thermodynamic chemical disequilibrium in Solar System atmospheres, in which we quantify the available Gibbs energy: the Gibbs free energy of an observed atmosphere minus that of atmospheric gases reacted to equilibrium. The purely gas phase disequilibrium in Earth's atmosphere is mostly attributable to O2 and CH4. The available Gibbs energy is not unusual compared to other Solar System atmospheres and smaller than that of Mars. However, Earth's fluid envelope contains an ocean, allowing gases to react with water and requiring a multiphase calculation with aqueous species. The disequilibrium in Earth's atmosphere-ocean system (in joules per mole of atmosphere) ranges from 20 to 2E6 times larger than the disequilibria of other atmospheres in the Solar System. Only on Earth is the chemical disequilibrium energy comparable to the thermal energy per mole of atmosphere. Earth's disequilibrium is biogenic, mainly caused by the coexistence of N2, O2 and liquid water instead of more stable nitrate. In comparison, the O2-CH4 disequilibrium is minor. We identify abiotic processes that cause disequilibrium in the other atmospheres. Our metric requires minimal assumptions and could potentially be calculated using observations of exoplanet atmospheres. However, further work is needed to establish whether thermodynamic disequilibrium is a practical exoplanet biosignature, requiring an assessment of false positives, noisy observations, and other detection challenges. Our Matlab code and databases for these calculations are available, open source.
Chemical disequilibrium in exoplanetary atmospheres (detectable with remote spectroscopy) can indicate life. The modern Earth's atmosphere-ocean system has a much larger chemical disequilibrium than other solar system planets with atmospheres because of oxygenic photosynthesis. However, no analysis exists comparing disequilibrium on lifeless, prebiotic planets to disequilibrium on worlds with primitive chemotrophic biospheres that live off chemicals and not light. Here, we use a photochemical-microbial ecosystem model to calculate the atmosphere-ocean disequilibria of Earth with no life and wi…
Phosphorus is an essential element for life, and the phosphorous cycle is widely believed to be a key factor limiting the extent of Earth's biosphere and its impact on remotely detectable features of Earth's atmospheric chemistry. Continental weathering is conventionally considered to be the only source of bioavailable phosphorus to the marine biosphere, with submarine hydrothermal processes acting as a phosphorus sink. Here, we use a novel 29Si tracer technique to demonstrate that alteration of submarine basalt under anoxic conditions leads to significant soluble phosphorus release, with an e…
Chemical disequilibrium has recently become a relevant topic in the study of the atmospheres of of transiting extrasolar planets, brown dwarfs, and directly imaged exoplanets. We present a new way of assessing whether or not a Jovian-like atmosphere is in chemical disequilibrium from observations of detectable or inferred gases such as H$_2$O, CH$_4$, CO, and H$_2$. Our hypothesis, based on previous kinetic modeling studies, is that cooler atmospheres will show stronger signs of disequilibrium than hotter atmospheres. We verify this with chemistry-transport models and show that planets with te…
The search for habitable exoplanets inspires the question - how do habitable planets form? Planet habitability models traditionally focus on abiotic processes and neglect a biotic response to changing conditions on an inhabited planet. The Gaia hypothesis postulates that life influences the Earth's feedback mechanisms to form a self-regulating system, and hence that life can maintain habitable conditions on its host planet. If life has a strong influence, it will have a role in determining a planet's habitability over time. We present the ExoGaia model - a model of simple 'planets' host to evo…
We develop a classification scheme for the evolutionary state of planets based on the non-equilibrium thermodynamics of their coupled systems, including the presence of a biosphere and the possibility of what we call an agency-dominated biosphere (i.e. an energy-intensive technological species). The premise is that Earths entry into the Anthropocene represents what might be from an astrobiological perspective a predictable planetary transition. We explore this problem from the perspective of the solar system and exoplanet studies. Our classification discriminates planets by the forms of free e…
Understanding the evolution of Earth and potentially habitable Earth-like worlds is essential to fathom our origin in the Universe. The search for Earth-like planets in the habitable zone and investigation of their atmospheres with climate and photochemical models is a central focus in exoplanetary science. Taking the evolution of Earth as a reference for Earth-like planets, a central scientific goal is to understand what the interactions were between atmosphere, geology, and biology on early Earth. The Great Oxidation Event (GOE) in Earth's history was certainly caused by their interplay, but…
Earth-like planets orbiting M-dwarfs are prominent future targets when searching for life outside the solar system. We apply our newly developed Coupled Atmosphere Biogeochemistry model to investigate the coupling between the biosphere, geosphere and atmosphere to gain deeper insight into the atmospheric evolution of Earth-like planets orbiting M-dwarfs. Our main goal is to understand better atmospheric processes affecting biosignatures and climate on such worlds. Furthermore, this is the first study to our knowledge which applies an automated chemical pathway analysis quantifying the producti…
Disequilibrium chemical processes have a large effect upon the spectra of substellar objects. To study these effects, dynamical disequilibrium has been parameterized using the quench and eddy diffusion approximations, but little work has been done to explore how these approximations perform under realistic planetary conditions in different dynamical regimes. As a first step in addressing this problem, we study the localized, small scale convective dynamics of planetary atmospheres by direct numerical simulation of fully compressible hydrodynamics with reactive tracers using the Dedalus code. U…
Ocean-atmosphere chemistry on Earth has undergone dramatic evolutionary changes through its long history, with potentially significant ramifications for the emergence and long-term stability of atmospheric biosignatures. Though a great deal of work has centered on refining our understanding of false positives for remote life detection, much less attention has been paid to the possibility of false negatives, that is, cryptical biospheres that are widespread and active on a planet's surface but are ultimately undetectable or difficult to detect in the composition of a planet's atmosphere. Here, …
The circumstellar habitable zone and its various refinements serves as a useful entry point for discussing the potential for a planet to generate and sustain life. But little attention is paid to the quality of available energy in the form of stellar photons for phototrophic (e.g. photosynthetic) life. This short paper discusses the application of the concept of exergy to exoplanetary environments and the evaluation of the maximum efficiency of energy use, or maximum work obtainable from electromagnetic radiation. Hotter stars provide temperate planets with higher maximum obtainable work with …
We aim to see if the difference between equilibrium and disequilibrium chemistry is observable in the atmospheres of transiting planets by the James Webb Space Telescope (JWST). We perform a case study comparing the dayside emission spectra of three planets like HD 189733b, WASP-80b, and GJ436b, in and out of chemical equilibrium at two metallicities each. These three planets were chosen because they span a large range of planetary masses and equilibrium temperatures, from hot and Jupiter-sized to warm and Neptune-sized. We link the one-dimensional disequilibrium chemistry model from Venot et …
Chemical disequilibrium in planetary atmospheres has been proposed as a generalized method for detecting life on exoplanets through remote spectroscopy. Among solar system planets with substantial atmospheres, the modern Earth has the largest thermodynamic chemical disequilibrium due to the presence of life. However, how this disequilibrium changed over time and, in particular, the biogenic disequilibria maintained in the anoxic Archean or less oxic Proterozoic eons are unknown. We calculate the atmosphere-ocean disequilibrium in the Precambrian using conservative proxy- and model-based estima…
The nearby TRAPPIST-1 planetary system is an exciting target for characterizing the atmospheres of terrestrial planets. The planets e, f and g lie in the circumstellar habitable zone and could sustain liquid water on their surfaces. During the extended pre-main sequence phase of TRAPPIST-1, however, the planets may have experienced extreme water loss, leading to a desiccated mantle. The presence or absence of an ocean is challenging to determine with current and next generation telescopes. Therefore, we investigate whether indirect evidence of an ocean and/or a biosphere can be inferred from o…
Massachusetts Institute of Technology（麻省理工学院）；Cardiff University（卡迪夫大学）；Indian Institute of Technology Kanpur（坎普尔印度理工学院）；Wroclaw University of Science and Technology（弗罗茨瓦夫科技大学）；JJ Scientific（JJ科学）
The search for signs of life through the detection of exoplanet atmosphere biosignature gases is gaining momentum. Yet, only a handful of rocky exoplanet atmospheres are suitable for observation with planned next-generation telescopes. To broaden prospects, we describe the possibilities for an aerial, liquid water cloud-based biosphere in the atmospheres of sub Neptune-sized temperate exoplanets, those receiving Earth-like irradiation from their host stars. One such planet is known (K2-18b) and other candidates are being followed up. Sub Neptunes are common and easier to study observationally …
A major motivation of spectroscopic observations of giant exoplanets is to unveil planet formation processes from atmospheric compositions. Several recent studies suggested that atmospheric nitrogen, like carbon and oxygen, can provide important constrains on planetary formation environments. Since nitrogen chemistry can be far from thermochemical equilibrium in warm atmospheres, we extensively investigate under what conditions, and with what assumptions, the observable NH3 abundances can diagnose an atmosphere's bulk nitrogen abundance. In the first paper of this series, we investigate atmosp…
In this work we study the effect of disequilibrium processes on mixing ratio profiles of neutral species and on the simulated spectra of a hot Jupiter exoplanet that orbits stars of different spectral types. We also address the impact of stellar activity that should be present to a different degree in all stars with convective envelopes. We used the VULCAN chemical kinetic code to compute number densities of species. The temperature-pressure profile of the atmosphere was computed with the HELIOS code. We also utilized the $τ$-ReX forward model to predict the spectra of planets in primary and s…
Almost all planetary atmospheres are affected by disequilibrium chemical processes. In this paper we introduce our recently developed Chemical Kinetic Model (\texttt{ChemKM}). We show that the results of our HD189733b model are in good agreement with previously published results, except at $μ$bar regime, where molecular diffusion and photochemistry are the dominant processes. We thus recommend careful consideration of these processes when abundances at the top of the atmosphere are desired. We also propose a new metric for a quantitative measure of quenching levels. By applying this metric, we…
With the characterisations of potentially habitable planetary atmospheres on the horizon, the search for biosignatures is set to become a major area of research in the coming decades. To understand the atmospheric characteristics that might indicate alien life we must understand the abiotic characteristics of a planet and how life interacts with its environment. In the field of biogeochemistry, sophisticated models of life-environment coupled systems demonstrate that many assumptions specific to Earth-based life, e.g. specific ATP maintenance costs, are unnecessary to accurately model a biosph…
Nitrogen is a major nutrient for all life on Earth and could plausibly play a similar role in extraterrestrial biospheres. The major reservoir of nitrogen at Earth's surface is atmospheric N2, but recent studies have proposed that the size of this reservoir may have fluctuated significantly over the course of Earth's history with particularly low levels in the Neoarchean - presumably as a result of biological activity. We used a biogeochemical box model to test which conditions are necessary to cause large swings in atmospheric N2 pressure. Parameters for our model are constrained by observati…
[Abridged] Aims. We present a large atmospheric study of 49 gas giant exoplanets using infrared transmission photometry with Spitzer/IRAC at 3.6 and 4.5um. Methods. We uniformly analyze 70 photometric light curves of 33 transiting planets using our custom pipeline, which implements pixel level decorrelation. We use this survey to understand how infrared photometry traces changes in atmospheric chemical properties as a function of planetary temperature. We compare our measurements to a grid of 1D radiative-convective equilibrium forward atmospheric models which include disequilibrium chemistry.…
Methane has been proposed as an exoplanet biosignature. Imminent observations with the James Webb Space Telescope may enable methane detections on potentially habitable exoplanets, so it is essential to assess in what planetary contexts methane is a compelling biosignature. Methane's short photochemical lifetime in terrestrial planet atmospheres implies that abundant methane requires large replenishment fluxes. While methane can be produced by a variety of abiotic mechanisms such as outgassing, serpentinizing reactions, and impacts, we argue that, in contrast to an Earth-like biosphere, known …
The emergence of oxygenic photosynthesis created a new niche with dramatic potential to transform energy flow through Earth's biosphere. However, more primitive forms of photosynthesis that fix CO2 into biomass using electrons from reduced species like Fe(II) and H2 instead of water would have competed with Earth's early oxygenic biosphere for essential nutrients. Here, we combine experimental microbiology, genomic analyses, and Earth system modeling to demonstrate that competition for light and nutrients in the surface ocean between oxygenic phototrophs and Fe(II)-oxidizing, anoxygenic photos…
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-μm water vapour band, leaving the planet's atmospheric composition poorly constrained. Her…
This past decade has seen tremendous advancements in the study of extrasolar planets. Observations are now made with increasing sophistication from both ground and space-based instruments, and exoplanets are characterized with increasing precision. There is a class of particularly interesting exoplanets, falling in the habitable zone, which is defined as the area around a star where the planet is capable of supporting liquid water on its surface. Theoretical calculations also suggest that close-in exoplanets are more likely to have weaker planetary magnetic fields, especially in case of super …
Inferences of molecular compositions of exoplanetary atmospheres have generally focused on C, H, and O-bearing molecules. Recently, additional absorption in HST WFC3 transmission spectra around 1.55$μ$m has been attributed to nitrogen-bearing chemical species: NH$_3$ or HCN. These species, if present in significant abundance, would be strong indicators of disequilibrium chemical processes -- e.g. vertical mixing and photochemistry. The derived N abundance, in turn, could also place important constraints on planetary formation mechanisms. Here, we examine the detectability of nitrogen chemistry…
Earth's modern atmosphere is highly oxygenated and is a remotely detectable signal of its surface biosphere. However, the lifespan of oxygen-based biosignatures in Earth's atmosphere remains uncertain, particularly for the distant future. Here we use a combined biogeochemistry and climate model to examine the likely timescale of oxygen-rich atmospheric conditions on Earth. Using a stochastic approach, we find that the mean future lifespan of Earth's atmosphere with oxygen levels more than 1% of the present atmospheric level is 1.08+-0.14 billion years. The model projects that a deoxygenation o…
Detection of life on other planets requires identification of biosignatures, i.e., observable planetary properties that robustly indicate the presence of a biosphere. One of the most widely accepted biosignatures for an Earth-like planet is an atmosphere where oxygen is a major constituent. Here we show that lifeless habitable zone terrestrial planets around any star type may develop oxygen-dominated atmospheres as a result of water photolysis, because the cold trap mechanism that protects H2O on Earth is ineffective when the atmospheric inventory of non-condensing gases (e.g., N2, Ar) is low.…
Chemical kinetics plays an important role in controlling the atmospheric composition of all planetary atmospheres, including those of extrasolar planets. For the hottest exoplanets, the composition can closely follow thermochemical-equilibrium predictions, at least in the visible and infrared photosphere at dayside (eclipse) conditions. However, for atmospheric temperatures < ~2000 K, and in the uppermost atmosphere at any temperature, chemical kinetics matters. The two key mechanisms by which kinetic processes drive an exoplanet atmosphere out of equilibrium are photochemistry and transport-i…
Institute of Space Research, German Aerospace Center (DLR)（德国航空航天中心空间研究所）；Astrophysics Division, NASA Goddard Space Flight Center（NASA戈达德太空飞行中心天体物理学部）；NASA Goddard Institute for Space Studies（NASA戈达德空间研究所）；Instituto Dom Luiz, Faculty of Sciences, University of Lisbon（里斯本大学理学院多姆·卢伊什研究所）；Earth and Planets Laboratory, Carnegie Institution for Science（卡内基科学学会地球与行星实验室）；Department of Earth Sciences, FU Berlin（柏林自由大学地球科学系）；Department of Earth, Environmental, and Planetary Sciences, Washington University（华盛顿大学地球、环境与行星科学系）；Planetary Science Institute, The Australian National University（澳大利亚国立大学行星科学研究所）
We present a new approach to exoplanet characterisation using techniques from complexity science, with potential applications to biosignature detection. This agnostic method makes use of the temporal variability of light reflected or emitted from a planet. We use a technique known as epsilon machine reconstruction to compute the statistical complexity, a measure of the minimal model size for time series data. We demonstrate that statistical complexity is an effective measure of the complexity of planetary features. Increasing levels of qualitative planetary complexity correlate with increases …
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 …
In Zhang $\&$ Showman (2018, hereafter Paper I), we developed an analytical theory of 1D eddy diffusivity $K_{zz}$ for global-mean vertical tracer transport in a 3D atmosphere. We also presented 2D numerical simulations on fast-rotating planets to validate our theory. On a slowly rotating planet such as Venus or a tidally locked planet (not necessarily a slow-rotator) such as a hot Jupiter, the tracer distribution could exhibit significant longitudinal inhomogeneity and tracer transport is intrinsically 3D. Here we study the global-mean vertical tracer transport on tidally locked planets using…
Here we review how environmental context can be used to interpret whether O2 is a biosignature in extrasolar planetary observations. This paper builds on the overview of current biosignature research discussed in Schwieterman et al. (2017), and provides an in-depth, interdisciplinary example of biosignature identification and observation that serves as a basis for the development of the general framework for biosignature assessment described in Catling et al., (2017). O2 is a potentially strong biosignature that was originally thought to be an unambiguous indicator for life at high-abundance. …
The formation of clouds affects brown dwarf and planetary atmospheres of nearly all effective temperatures. Iron and silicate condense in L dwarf atmospheres and dissipate at the L/T transition. Minor species such as sulfides and salts condense in mid-late T dwarfs. For brown dwarfs below Teff=450 K, water condenses in the upper atmosphere to form ice clouds. Currently over a dozen objects in this temperature range have been discovered, and few previous theoretical studies have addressed the effect of water clouds on brown dwarf or exoplanetary spectra. Here we present a new grid of models tha…
Understanding whether M-dwarf stars may host habitable planets with Earth-like atmospheres and biospheres is a major goal in exoplanet research. If such planets exist, the question remains as to whether they could be identified via spectral signatures of biomarkers. Such planets may be exposed to extreme intensities of cosmic rays that could perturb their atmospheric photochemistry. Here, we consider stellar activity of M-dwarfs ranging from quiet up to strong flaring conditions and investigate one particular effect upon biomarkers, namely, the ability of secondary electrons caused by stellar …
In the coming years and decades, advanced space- and ground-based observatories will allow an unprecedented opportunity to probe the atmospheres and surfaces of potentially habitable exoplanets for signatures of life. Life on Earth, through its gaseous products and reflectance and scattering properties, has left its fingerprint on the spectrum of our planet. Aided by the universality of the laws of physics and chemistry, we turn to Earth's biosphere, both in the present and through geologic time, for analog signatures that will aid in the search for life elsewhere. Considering the insights gai…
Resolving Orbital and Climate Keys of Earth and Extraterrestrial Environments with Dynamics (ROCKE-3D) is a 3-Dimensional General Circulation Model (GCM) developed at the NASA Goddard Institute for Space Studies for the modeling of atmospheres of Solar System and exoplanetary terrestrial planets. Its parent model, known as ModelE2 (Schmidt et al. 2014), is used to simulate modern and 21st Century Earth and near-term paleo-Earth climates. ROCKE-3D is an ongoing effort to expand the capabilities of ModelE2 to handle a broader range of atmospheric conditions including higher and lower atmospheric…
Probing Exoplanetary Chemistry with Ariel: Scientific Priorities and Observational Strategies
Univ. Grenoble Alpes CNRS IPAG（格勒诺布尔阿尔卑斯大学法国国家科学研究中心IPAG实验室）；Université Paris Cité and Univ Paris Est Creteil CNRS LISA（巴黎西岱大学和巴黎东 Créteil大学法国国家科学研究中心LISA实验室）；SRON Netherlands Institute for Space Research（荷兰空间研究所）；Leiden Observatory Leiden University（莱顿大学莱顿天文台）；Anton Pannekoek Institute for Astronomy University of Amsterdam（阿姆斯特丹大学安东·潘内克天文学研究所）；IRAP Université de Toulouse CNRS/UMR 5277 UPS-OMP（图卢兹大学法国国家科学研究中心IRAP研究所）；Institute（研究所）
Detailed characterization of an extrasolar planet's atmosphere provides the best hope for distinguishing the makeup of its outer layers, and the only hope for understanding the interplay between initial composition, chemistry, dynamics & circulation, and disequilibrium processes. In recent years, some areas have seen rapid progress while developments in others have come more slowly and/or have been hotly contested. This article gives an observer's perspective on the current understanding of extrasolar planet atmospheres prior to the considerable advances expected from the next generation of ob…
Rocky planets are common around other stars, but their atmospheric properties remain largely unconstrained. Thanks to a wealth of recent planet discoveries and upcoming advances in observing capability, we are poised to characterize the atmospheres of dozens of rocky exoplanets in this decade. Theoretical understanding of rocky exoplanet atmospheres has advanced considerably in the last few years, yielding testable predictions of their evolution, chemistry, dynamics and even possible biosignatures. Here we review key progress in this field to date and discuss future objectives. Our major concl…
The atmospheres of synchronously rotating exoplanets are intrinsically three-dimensional, and fast vertical and horizontal winds are expected to mix the atmosphere, driving the chemical composition out of equilibrium. Due to the longer computation times associated with multi-dimensional forward models, horizontal mixing has only been investigated for a few case studies. In this paper, we aim to generalize the impact of horizontal and vertical mixing on the chemistry of exoplanet atmospheres over a large parameter space. We do this by applying a sequence of post-processed forward models for a l…
Detections of molecules in the atmosphere of gas giant exoplanets allow us to investigate the physico-chemical properties of the atmospheres. Their inferred chemical composition is used as tracer of planet formation and evolution mechanisms. Currently, an increasing number of detections is showing a possible rich chemistry of the hotter gaseous planets, but whether this extends to cooler giants is still unknown. We observed four transits of WASP-80 b, a warm transiting giant planet orbiting a late-K dwarf star with the near-infrared GIANO-B spectrograph installed at the Telescopio Nazionale Ga…
Transmission spectroscopy is enabling precise measurements of atmospheric H2O abundances for numerous giant exoplanets. For hot Jupiters, relating H2O abundances to metallicities provides a powerful probe of their formation conditions. However, metallicity measurements for Neptune-mass exoplanets are only now becoming viable. Exo-Neptunes are expected to possess super-solar metallicities from accretion of H2O-rich and solid-rich planetesimals. However, initial investigations into the exo-Neptune HAT-P-26b suggested a significantly lower metallicity than predicted by the core-accretion theory o…
Photosynthetic exergy I. Thermodynamic limits for habitable-zone planets
Università di Napoli Federico II（那不勒斯费德里科二世大学）；INFN, Sezione di Napoli（意大利国家核物理研究所那不勒斯分部）；INAF – Osservatorio Astronomico di Capodimonte（意大利国家天体物理研究所卡波迪蒙特天文台）；Università di Roma Tor Vergata（罗马托维加塔大学）
