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 gained from modern and ancient Earth, and the broader array of hypothetical exoplanet possibilities, we have compiled a comprehensive overview of our current understanding of potential exoplanet biosignatures, including gaseous, surface, and temporal biosignatures. We additionally survey biogenic spectral features that are well known in the specialist literature but have not yet been robustly vetted in the context of exoplanet biosignatures. We briefly review advances in assessing biosignature plausibility, including novel methods for determining chemical disequilibrium from remotely obtainable data and assessment tools for determining the minimum biomass required to maintain short-lived biogenic gases as atmospheric signatures. We focus particularly on advances made since the seminal review by Des Marais et al. The purpose of this work is not to propose new biosignature strategies, a goal left to companion articles in this series, but to review the current literature, draw meaningful connections between seemingly disparate areas, and clear the way for a path forward. Key Words: Exoplanets—Biosignatures—Habitability markers—Photosynthesis—Planetary surfaces—Atmospheres—Spectroscopy—Cryptic biospheres—False positives. Astrobiology 18, 663–708.

Recognizing whether a planet can support life is a primary goal of future exoplanet spectral characterization missions, but past research on habitability assessment has largely ignored the vastly different conditions that have existed in our planet's long habitable history. This study presents simulations of a habitable yet dramatically different phase of Earth's history, when the atmosphere contained a Titan-like, organic-rich haze. Prior work has claimed a haze-rich Archean Earth (3.8–2.5 billion years ago) would be frozen due to the haze's cooling effects. However, no previous studies have self-consistently taken into account climate, photochemistry, and fractal hazes. Here, we demonstrate using coupled climate-photochemical-microphysical simulations that hazes can cool the planet's surface by about 20 K, but habitable conditions with liquid surface water could be maintained with a relatively thick haze layer (τ ∼ 5 at 200 nm) even with the fainter young Sun. We find that optically thicker hazes are self-limiting due to their self-shielding properties, preventing catastrophic cooling of the planet. Hazes may even enhance planetary habitability through UV shielding, reducing surface UV flux by about 97% compared to a haze-free planet and potentially allowing survival of land-based organisms 2.7–2.6 billion years ago. The broad UV absorption signature produced by this haze may be visible across interstellar distances, allowing characterization of similar hazy exoplanets. The haze in Archean Earth's atmosphere was strongly dependent on biologically produced methane, and we propose that hydrocarbon haze may be a novel type of spectral biosignature on planets with substantial levels of CO2. Hazy Archean Earth is the most alien world for which we have geochemical constraints on environmental conditions, providing a useful analogue for similar habitable, anoxic exoplanets. Key Words: Haze—Archean Earth—Exoplanets—Spectra—Biosignatures—Planetary habitability. Astrobiology 16, 873–899.

In the search for life on Earth-like planets around other stars, the first (and likely only) information will come from the spectroscopic characterization of the planet's atmosphere. Of the countless number of chemical species terrestrial life produces, only a few have the distinct spectral features and the necessary atmospheric abundance to be detectable. The easiest of these species to observe in Earth's atmosphere is O 2 (and its photochemical byproduct, O 3 ). But O 2 can also be produced abiotically by photolysis of CO 2 , followed by recombination of O atoms with each other. CO is produced in stoichiometric proportions. Whether O 2 and CO can accumulate to appreciable concentrations depends on the ratio of far-UV to near-UV radiation coming from the planet's parent star and on what happens to these gases when they dissolve in a planet's oceans. Using a one-dimensional photochemical model, we demonstrate that O 2 derived from CO 2 photolysis should not accumulate to measurable concentrations on planets around F-and G-type stars. K-star, and especially M-star planets, however, may build up O 2 because of the low near-UV flux from their parent stars, in agreement with some previous studies. On such planets, a 'false positive' for life is possible if recombination of dissolved CO and O 2 in the oceans is slow and if other O 2 sinks (e.g., reduced volcanic gases or dissolved ferrous iron) are small. O 3 , on the other hand, could be detectable at UV wavelengths (λ < 300 nm) for a much broader range of boundary conditions and stellar types.Subject headings: planets and satellites: atmospheres -planets and satellites: terrestrial planets -planetstar interactions -ultraviolet: planetary systems

We describe how environmental context can help determine whether oxygen (O2) detected in extrasolar planetary observations is more likely to have a biological source. Here we provide an in-depth, interdisciplinary example of O2 biosignature identification and observation, which serves as the prototype for the development of a general framework for biosignature assessment. Photosynthetically generated O2 is a potentially strong biosignature, and at high abundance, it was originally thought to be an unambiguous indicator for life. However, as a biosignature, O2 faces two major challenges: (1) it was only present at high abundance for a relatively short period of Earth's history and (2) we now know of several potential planetary mechanisms that can generate abundant O2 without life being present. Consequently, our ability to interpret both the presence and absence of O2 in an exoplanetary spectrum relies on understanding the environmental context. Here we examine the coevolution of life with the early Earth's environment to identify how the interplay of sources and sinks may have suppressed O2 release into the atmosphere for several billion years, producing a false negative for biologically generated O2. These studies suggest that planetary characteristics that may enhance false negatives should be considered when selecting targets for biosignature searches. We review the most recent knowledge of false positives for O2, planetary processes that may generate abundant atmospheric O2 without a biosphere. We provide examples of how future photometric, spectroscopic, and time-dependent observations of O2 and other aspects of the planetary environment can be used to rule out false positives and thereby increase our confidence that any observed O2 is indeed a biosignature. These insights will guide and inform the development of future exoplanet characterization missions. Key Words: Biosignatures—Oxygenic photosynthesis—Exoplanets—Planetary atmospheres. Astrobiology 18, 630–662.

Hazes are common in known planet atmospheres, and geochemical evidence suggests early Earth occasionally supported an organic haze with significant environmental and spectral consequences. The UV spectrum of the parent star drives organic haze formation through methane photochemistry. We use a 1D photochemical-climate model to examine production of fractal organic haze on Archean Earthanalogs in the habitable zonesof several stellar types: the modern and early Sun, AD Leo (M3.5V), GJ 876 (M4V), Eridani (K2V), and σ Boötis (F2V). For Archean-like atmospheres, planets orbiting stars with the highest UV fluxes do not form haze due to the formation of photochemical oxygen radicals that destroy haze precursors. Organic hazes impact planetary habitability via UV shielding and surface cooling, but this cooling is minimized around M dwarfs whose energy is emitted at wavelengths where organic hazes are relatively transparent. We generate spectra to test the detectability of haze. For 10 transits of a planet orbiting GJ 876 observed by the James Webb Space Telescope, haze makes gaseous absorption features at wavelengths < 2.5 µm 2-10σ shallower compared to a haze-free planet, and methane and carbon dioxide are detectable at >5σ. A haze absorption feature can be detected at 5σ near 6.3 µm, but higher signal-to-noise is needed to distinguish haze from adjacent absorbers. For direct imaging of a planet at 10 parsecs using a coronagraphic 10-meter class ultraviolet-visible-near infrared telescope, a UV-blue haze absorption feature would be strongly detectable at >12σ in 200 hours.

Proxima Centauri b provides an unprecedented opportunity to understand the evolution and nature of terrestrial planets orbiting M dwarfs. Although Proxima Cen b orbits within its star's habitable zone, multiple plausible evolutionary paths could have generated different environments that may or may not be habitable. Here, we use 1-D coupled climate-photochemical models to generate self-consistent atmospheres for several evolutionary scenarios, including high-O2, high-CO2, and more Earth-like atmospheres, with both oxic and anoxic compositions. We show that these modeled environments can be habitable or uninhabitable at Proxima Cen b's position in the habitable zone. We use radiative transfer models to generate synthetic spectra and thermal phase curves for these simulated environments, and use instrument models to explore our ability to discriminate between possible planetary states. These results are applicable not only to Proxima Cen b but to other terrestrial planets orbiting M dwarfs. Thermal phase curves may provide the first constraint on the existence of an atmosphere. We find that James Webb Space Telescope (JWST) observations longward of 10 μm could characterize atmospheric heat transport and molecular composition. Detection of ocean glint is unlikely with JWST but may be within the reach of larger-aperture telescopes. Direct imaging spectra may detect O4 absorption, which is diagnostic of massive water loss and O2 retention, rather than a photosynthetic biosphere. Similarly, strong CO2 and CO bands at wavelengths shortward of 2.5 μm would indicate a CO2-dominated atmosphere. If the planet is habitable and volatile-rich, direct imaging will be the best means of detecting habitability. Earth-like planets with microbial biospheres may be identified by the presence of CH4—which has a longer atmospheric lifetime under Proxima Centauri's incident UV—and either photosynthetically produced O2 or a hydrocarbon haze layer. Key Words: Planetary habitability and biosignatures—Planetary atmospheres—Exoplanets—Spectroscopic biosignatures—Planetary science—Proxima Centauri b. Astrobiology 18, 133–189.

Characterizing the bulk atmosphere of a terrestrial planet is important for determining surface pressure and potential habitability. Molecular nitrogen (N 2) constitutes the largest fraction of Earth's atmosphere and is likely to be a major constituent of many terrestrial exoplanet atmospheres. Due to its lack of significant absorption features, N 2 is extremely difficult to remotely detect. However, N 2 produces an N 2-N 2 collisional pair, (N 2) 2 , which is spectrally active. Here we report the detection of (N 2) 2 in Earth's disk-integrated spectrum. By comparing spectra from NASA's EPOXI mission to synthetic spectra from the NASA Astrobiology Institute's Virtual Planetary Laboratory three-dimensional spectral Earth model, we find that (N 2) 2 absorption produces a ~35% decrease in flux at 4.15 µm. Quantifying N 2 could provide a means of determining bulk atmospheric composition for terrestrial exoplanets and could rule out abiotic O 2 generation, which is possible in rarefied atmospheres. To explore the potential effects of (N 2) 2 in exoplanet spectra, we used radiative transfer models to generate synthetic emission and transit transmission spectra of self-consistent N 2-CO 2-H 2 O atmospheres, and analytic N 2-H 2 and N 2-H 2-CO 2 atmospheres. We show that (N 2) 2 absorption in the wings of the 4.3 µm CO 2 band is strongly dependent on N 2 partial pressures above 0.5 bar and can significantly widen this band in thick N 2 atmospheres. The (N 2) 2 transit transmission signal is up to 10 ppm for an Earth-size planet with an N 2-dominated atmosphere orbiting within the HZ of an M5V star and could be substantially larger for planets with significant H 2 mixing ratios.

We introduce a Bayesian method for guiding future directions for detection of life on exoplanets. We describe empirical and theoretical work necessary to place constraints on the relevant likelihoods, including those emerging from better understanding stellar environment, planetary climate and geophysics, geochemical cycling, the universalities of physics and chemistry, the contingencies of evolutionary history, the properties of life as an emergent complex system, and the mechanisms driving the emergence of life. We provide examples for how the Bayesian formalism could guide future search strategies, including determining observations to prioritize or deciding between targeted searches or larger lower resolution surveys to generate ensemble statistics and address how a Bayesian methodology could constrain the prior probability of life with or without a positive detection. Key Words: Exoplanets—Biosignatures—Life detection—Bayesian analysis. Astrobiology 18, 779–824.