The case and context for atmospheric methane as an exoplanet biosignature.

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 that­in contrast to an Earth-like biosphere­known abiotic processes cannot easily generate atmospheres rich in CH4 and CO2 with limited CO due to the strong redox disequilibrium between CH4 and CO2. Methane is thus more likely to be biogenic for planets with 1) a terrestrial bulk density, high mean-molecular-weight and anoxic atmosphere, and an old host star; 2) an abundance of CH4 that implies surface fluxes exceeding what could be supplied by abiotic processes; and 3) atmospheric CO2 with comparatively little CO.

Carbon cycle inverse modeling suggests large changes in fractional organic burial are consistent with the carbon isotope record and may have contributed to the rise of oxygen.

Abundant geologic evidence shows that atmospheric oxygen levels were negligible until the Great Oxidation Event (GOE) at 2.4-2.1 Ga. The burial of organic matter is balanced by the release of oxygen, and if the release rate exceeds efficient oxygen sinks, atmospheric oxygen can accumulate until limited by oxidative weathering. The organic burial rate relative to the total carbon burial rate can be inferred from the carbon isotope record in sedimentary carbonates and organic matter, which provides a proxy for the oxygen source flux through time. Because there are no large secular trends in the carbon isotope record over time, it is commonly assumed that the oxygen source flux changed only modestly. Therefore, declines in oxygen sinks have been used to explain the GOE. However, the average isotopic value of carbon fluxes into the atmosphere-ocean system can evolve due to changing proportions of weathering and outgassing inputs. If so, large secular changes in organic burial would be possible despite unchanging carbon isotope values in sedimentary rocks. Here, we present an inverse analysis using a self-consistent carbon cycle model to determine the maximum change in organic burial since ~4 Ga allowed by the carbon isotope record and other geological proxies. We find that fractional organic burial may have increased by 2-5 times since the Archean. This happens because O2 -dependent continental weathering of 13 C-depleted organics changes carbon isotope inputs to the atmosphere-ocean system. This increase in relative organic burial is consistent with an anoxic-to-oxic atmospheric transition around 2.4 Ga without declining oxygen sinks, although these likely contributed. Moreover, our inverse analysis suggests that the Archean absolute organic burial flux was comparable to modern, implying high organic burial efficiency and ruling out very low Archean primary productivity.

Carbonate-silicate cycle predictions of Earth-like planetary climates and testing the habitable zone concept.

In the conventional habitable zone (HZ) concept, a CO2-H2O greenhouse maintains surface liquid water. Through the water-mediated carbonate-silicate weathering cycle, atmospheric CO2 partial pressure (pCO2) responds to changes in surface temperature, stabilizing the climate over geologic timescales. We show that this weathering feedback ought to produce a log-linear relationship between pCO2 and incident flux on Earth-like planets in the HZ. However, this trend has scatter because geophysical and physicochemical parameters can vary, such as land area for weathering and CO2 outgassing fluxes. Using a coupled climate and carbonate-silicate weathering model, we quantify the likely scatter in pCO2 with orbital distance throughout the HZ. From this dispersion, we predict a two-dimensional relationship between incident flux and pCO2 in the HZ and show that it could be detected from at least 83 (2σ) Earth-like exoplanet observations. If fewer Earth-like exoplanets are observed, testing the HZ hypothesis from this relationship could be difficult.

A Maximum Subsurface Biomass on Mars from Untapped Free Energy: CO and H2 as Potential Antibiosignatures.

Whether extant life exists in the martian subsurface is an open question. High concentrations of photochemically produced CO and H2 in the otherwise oxidizing martian atmosphere represent untapped sources of biologically useful free energy. These out-of-equilibrium species diffuse into the regolith, so subsurface microbes could use them as a source of energy and carbon. Indeed, CO oxidation and methanogenesis are relatively simple and evolutionarily ancient metabolisms on Earth. Consequently, assuming CO- or H2-consuming metabolisms would evolve on Mars, the persistence of CO and H2 in the martian atmosphere sets limits on subsurface metabolic activity. In this study, we constrain such maximum subsurface metabolic activity on Mars using a one-dimensional photochemical model with a hypothetical global biological sink on atmospheric CO and H2. We increase the biological sink until the modeled atmospheric composition diverges from observed abundances. We find maximum biological downward subsurface sinks of 1.5 × 108 molecules/(cm2·s) for CO and 1.9 × 108 molecules/(cm2·s1) for H2. These convert to a maximum metabolizing biomass of ≲1027 cells or ≤2 × 1011 kg, equivalent to ≤10-4-10-5 of Earth's biomass, depending on the terrestrial estimate. Diffusion calculations suggest that this upper biomass limit applies to the top few kilometers of the martian crust in communication with the atmosphere at low to mid-latitudes. This biomass limit is more robust than previous estimates because we test multiple possible chemoautotrophic ecosystems over a broad parameter space of tunable model variables using an updated photochemical model with precise atmospheric concentrations and uncertainties from Curiosity. Our results of sparse or absent life in the martian subsurface also demonstrate how the atmospheric redox pairs of CO-O2 and H2-O2 may constitute antibiosignatures, which may be relevant to excluding life on exoplanets.

Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model.

The early Earth's environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically justified temperature and pH dependence of seafloor weathering, allowing the relative importance of continental and seafloor weathering to be evaluated. We find that the Archean climate was likely temperate (0-50 °C) due to the combined negative feedbacks of continental and seafloor weathering. Ocean pH evolves monotonically from [Formula: see text] (2σ) at 4.0 Ga to [Formula: see text] (2σ) at the Archean-Proterozoic boundary, and to [Formula: see text] (2σ) at the Proterozoic-Phanerozoic boundary. This evolution is driven by the secular decline of pCO2, which in turn is a consequence of increasing solar luminosity, but is moderated by carbonate alkalinity delivered from continental and seafloor weathering. Archean seafloor weathering may have been a comparable carbon sink to continental weathering, but is less dominant than previously assumed, and would not have induced global glaciation. We show how these conclusions are robust to a wide range of scenarios for continental growth, internal heat flow evolution and outgassing history, greenhouse gas abundances, and changes in the biotic enhancement of weathering.

Exoplanet Biosignatures: A Framework for Their Assessment.

Finding life on exoplanets from telescopic observations is an ultimate goal of exoplanet science. Life produces gases and other substances, such as pigments, which can have distinct spectral or photometric signatures. Whether or not life is found with future data must be expressed with probabilities, requiring a framework of biosignature assessment. We present a framework in which we advocate using biogeochemical "Exo-Earth System" models to simulate potential biosignatures in spectra or photometry. Given actual observations, simulations are used to find the Bayesian likelihoods of those data occurring for scenarios with and without life. The latter includes "false positives" wherein abiotic sources mimic biosignatures. Prior knowledge of factors influencing planetary inhabitation, including previous observations, is combined with the likelihoods to give the Bayesian posterior probability of life existing on a given exoplanet. Four components of observation and analysis are necessary. (1) Characterization of stellar (e.g., age and spectrum) and exoplanetary system properties, including "external" exoplanet parameters (e.g., mass and radius), to determine an exoplanet's suitability for life. (2) Characterization of "internal" exoplanet parameters (e.g., climate) to evaluate habitability. (3) Assessment of potential biosignatures within the environmental context (components 1-2), including corroborating evidence. (4) Exclusion of false positives. We propose that resulting posterior Bayesian probabilities of life's existence map to five confidence levels, ranging from "very likely" (90-100%) to "very unlikely" (<10%) inhabited. Key Words: Bayesian statistics-Biosignatures-Drake equation-Exoplanets-Habitability-Planetary science. Astrobiology 18, 709-738.

Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life.

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 estimates of early atmospheric and oceanic compositions. We omit crustal solids because subsurface composition is not detectable on exoplanets, unlike above-surface volatiles. We find that (i) disequilibrium increased through time in step with the rise of oxygen; (ii) both the Proterozoic and Phanerozoic may have had remotely detectable biogenic disequilibria due to the coexistence of O2, N2, and liquid water; and (iii) the Archean had a biogenic disequilibrium caused by the coexistence of N2, CH4, CO2, and liquid water, which, for an exoplanet twin, may be remotely detectable. On the basis of this disequilibrium, we argue that the simultaneous detection of abundant CH4 and CO2 in a habitable exoplanet's atmosphere is a potential biosignature. Specifically, we show that methane mixing ratios greater than 10-3 are potentially biogenic, whereas those exceeding 10-2 are likely biogenic due to the difficulty in maintaining large abiotic methane fluxes to support high methane levels in anoxic atmospheres. Biogenicity would be strengthened by the absence of abundant CO, which should not coexist in a biological scenario.

Constraining climate sensitivity and continental versus seafloor weathering using an inverse geological carbon cycle model.

The relative influences of tectonics, continental weathering and seafloor weathering in controlling the geological carbon cycle are unknown. Here we develop a new carbon cycle model that explicitly captures the kinetics of seafloor weathering to investigate carbon fluxes and the evolution of atmospheric CO2 and ocean pH since 100 Myr ago. We compare model outputs to proxy data, and rigorously constrain model parameters using Bayesian inverse methods. Assuming our forward model is an accurate representation of the carbon cycle, to fit proxies the temperature dependence of continental weathering must be weaker than commonly assumed. We find that 15-31 °C (1σ) surface warming is required to double the continental weathering flux, versus 3-10 °C in previous work. In addition, continental weatherability has increased 1.7-3.3 times since 100 Myr ago, demanding explanation by uplift and sea-level changes. The average Earth system climate sensitivity is K (1σ) per CO2 doubling, which is notably higher than fast-feedback estimates. These conclusions are robust to assumptions about outgassing, modern fluxes and seafloor weathering kinetics.

On Detecting Biospheres from Chemical Thermodynamic Disequilibrium in Planetary Atmospheres.

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 2 × 10(6) times larger than the disequilibria of other atmospheres in the Solar System, where Mars is second to Earth. Only on Earth is the chemical disequilibrium energy comparable to the thermal energy per mole of atmosphere (excluding comparison to Titan with lakes, where quantification is precluded because the mean lake composition is unknown). 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, although kinetics requires a large CH4 flux into the atmosphere. We identify abiotic processes that cause disequilibrium in the other atmospheres. Our metric requires minimal assumptions and could potentially be calculated from 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.

Transient Sulfate Aerosols as a Signature of Exoplanet Volcanism.

Geological activity is thought to be important for the origin of life and for maintaining planetary habitability. We show that transient sulfate aerosols could be a signature of exoplanet volcanism and therefore of a geologically active world. A detection of transient aerosols, if linked to volcanism, could thus aid in habitability evaluations of the exoplanet. On Earth, subduction-induced explosive eruptions inject SO2 directly into the stratosphere, leading to the formation of sulfate aerosols with lifetimes of months to years. We demonstrate that the rapid increase and gradual decrease in sulfate aerosol loading associated with these eruptions may be detectable in transit transmission spectra with future large-aperture telescopes, such as the James Webb Space Telescope (JWST) and European Extremely Large Telescope (E-ELT), for a planetary system at a distance of 10 pc, assuming an Earth-like atmosphere, bulk composition, and size. Specifically, we find that a signal-to-noise ratio of 12.1 and 7.1 could be achieved with E-ELT (assuming photon-limited noise) for an Earth analogue orbiting a Sun-like star and M5V star, respectively, even without multiple transits binned together. We propose that the detection of this transient signal would strongly suggest an exoplanet volcanic eruption, if potential false positives such as dust storms or bolide impacts can be ruled out. Furthermore, because scenarios exist in which O2 can form abiotically in the absence of volcanic activity, a detection of transient aerosols that can be linked to volcanism, along with a detection of O2, would be a more robust biosignature than O2 alone.