We present a study of the photochemistry of abiotic habitable planets with anoxic CO$_2$-N$_2$ atmospheres. Such worlds are representative of early Earth, Mars and Venus, and analogous exoplanets. H$_2$O photodissociation controls the atmospheric photochemistry of these worlds through production of reactive OH, which dominates the removal of atmospheric trace gases. The near-UV (NUV; $>200$ nm) absorption cross-sections of H$_2$O play an outsized role in OH production; these cross-sections were heretofore unmeasured at habitable temperatures ($<373$ K). We present the first measurements of NUV H$_2$O absorption at $292$ K, and show it to absorb orders of magnitude more than previously assumed. To explore the implications of these new cross-sections, we employ a photochemical model; we first intercompare it with two others and resolve past literature disagreement. The enhanced OH production due to these higher cross-sections leads to efficient recombination of CO and O$_2$, suppressing both by orders of magnitude relative to past predictions and eliminating the low-outgassing "false positive" scenario for O$_2$ as a biosignature around solar-type stars. Enhanced [OH] increases rainout of reductants to the surface, relevant to prebiotic chemistry, and may also suppress CH$_4$ and H$_2$; the latter depends on whether burial of reductants is inhibited on the underlying planet, as is argued for abiotic worlds. While we focus on CO$_2$-rich worlds, our results are relevant to anoxic planets in general. Overall, our work advances the state-of-the-art of photochemical models by providing crucial new H$_2$O cross-sections and resolving past disagreement in the literature, and suggests that detection of spectrally active trace gases like CO in rocky exoplanet atmospheres may be more challenging than previously considered.

Abstract The habitable zone (HZ) is commonly defined as the range of distances from a host star within which liquid water, a key requirement for life, may exist on a planet’s surface. Substantially more CO2 than present in Earth’s modern atmosphere is required to maintain clement temperatures for most of the HZ, with several bars required at the outer edge. However, most complex aerobic life on Earth is limited by CO2 concentrations of just fractions of a bar. At the same time, most exoplanets in the traditional HZ reside in proximity to M dwarfs, which are more numerous than Sun-like G dwarfs but are predicted to promote greater abundances of gases that can be toxic in the atmospheres of orbiting planets, such as carbon monoxide (CO). Here we show that the HZ for complex aerobic life is likely limited relative to that for microbial life. We use a 1D radiative-convective climate and photochemical models to circumscribe a Habitable Zone for Complex Life (HZCL) based on known toxicity limits for a range of organisms as a proof of concept. We find that for CO2 tolerances of 0.01, 0.1, and 1 bar, the HZCL is only 21%, 32%, and 50% as wide as the conventional HZ for a Sun-like star, and that CO concentrations may limit some complex life throughout the entire HZ of the coolest M dwarfs. These results cast new light on the likely distribution of complex life in the universe and have important ramifications for the search for exoplanet biosignatures and technosignatures.

Abstract: Efforts to spectrally characterize the atmospheric compositions of temperate terrestrial exoplanets orbiting M dwarf stars with JWST are now underway. Key molecular targets of such searches include O2 and CO, which are potential indicators of life. Recently, it was proposed that CO2 photolysis generates abundant (≳0.1 bar) abiotic O2 and CO in the atmospheres of habitable M dwarf planets with CO2-rich atmospheres, constituting a strong false positive for O2 as a biosignature and further complicating efforts to use CO as a diagnostic of surface biology. Importantly, this implied that TRAPPIST-1e and TRAPPIST-1f, now under observation with JWST, would abiotically accumulate abundant O2 and CO, if habitable. Here, we use a multi-model approach to reexamine photochemical O2 and CO accumulation on planets orbiting M dwarf stars. We show that photochemical O2 remains a trace gas on habitable CO2-rich M dwarf planets, with earlier predictions of abundant O2 and CO due to an atmospheric model top that was too low to accurately resolve the unusually high CO2 photolysis peak on such worlds. Our work strengthens the case for O2 as a biosignature gas, and affirms the importance of CO as a diagnostic of photochemical O2 production. However, observationally relevant false-positive potential remains, especially for O2's photochemical product O3, and further work is required to confidently understand O2 and O3 as biosignature gases on M dwarf planets.

The habitable zone (HZ) is commonly defined as the range of distances from a host star within which liquid water, a key requirement for life, may exist on a planet's surface. Substantially more CO2 than present in Earth's modern atmosphere is required to maintain clement temperatures for most of the HZ, with several bars required at the outer edge. However, most complex aerobic life on Earth is limited by CO2 concentrations of just fractions of a bar. At the same time, most exoplanets in the traditional HZ reside in proximity to M dwarfs, which are more numerous than Sun-like G dwarfs but are predicted to promote greater abundances of gases that can be toxic in the atmospheres of orbiting planets, such as carbon monoxide (CO). Here we show that the HZ for complex aerobic life is likely limited relative to that for microbial life. We use a 1D radiative-convective climate and photochemical models to circumscribe a Habitable Zone for Complex Life (HZCL) based on known toxicity limits for a range of organisms as a proof of concept. We find that for CO2 tolerances of 0.01, 0.1, and 1 bar, the HZCL is only 21%, 32%, and 50% as wide as the conventional HZ for a Sun-like star, and that CO concentrations may limit some complex life throughout the entire HZ of the coolest M dwarfs. These results cast new light on the likely distribution of complex life in the universe and have important ramifications for the search for exoplanet biosignatures and technosignatures.

Some atmospheric gases have been proposed as counter indicators to the presence of life on an exoplanet if remotely detectable at sufficient abundance (i.e., antibiosignatures), informing the search for biosignatures and potentially fingerprinting uninhabited habitats. However, the quantitative extent to which putative antibiosignatures could exist in the atmospheres of inhabited planets is not well understood. The most commonly referenced potential antibiosignature is CO, because it represents a source of free energy and reduced carbon that is readily exploited by life on Earth and is thus often assumed to accumulate only in the absence of life. Yet, biospheres actively produce CO through biomass burning, photooxidation processes, and release of gases that are photochemically converted into CO in the atmosphere. We demonstrate with a 1D ecosphere-atmosphere model that reducing biospheres can maintain CO levels of ~100 ppmv even at low H2 fluxes due to the impact of hybrid photosynthetic ecosystems. Additionally, we show that photochemistry around M dwarf stars is particularly favorable for the buildup of CO, with plausible concentrations for inhabited, oxygen-rich planets extending from hundreds of ppm to several percent. Since CH4 buildup is also favored on these worlds, and because O2 and O3 are likely not detectable with the James Webb Space Telescope, the presence of high CO (>100 ppmv) may discriminate between oxygen-rich and reducing biospheres with near-future transmission observations. These results suggest that spectroscopic detection of CO can be compatible with the presence of life and that a comprehensive contextual assessment is required to validate the significance of potential antibiosignatures.

O2 and O3 have been long considered the most robust individual biosignature gases in a planetary atmosphere, yet multiple mechanisms that may produce them in the absence of life have been described. However, these abiotic planetary mechanisms modify the environment in potentially identifiable ways. Here we briefly discuss two of the most detectable spectral discriminants for abiotic O2/O3: CO and O4. We produce the first explicit self-consistent simulations of these spectral discriminants as they may be seen by James Webb Space Telescope (JWST). If JWST-NIRISS and/or NIRSpec observe CO (2.35, 4.6 μm) in conjunction with CO2 (1.6, 2.0, 4.3 μm) in the transmission spectrum of a terrestrial planet it could indicate robust CO2 photolysis and suggest that a future detection of O2 or O3 might not be biogenic. Strong O4 bands seen in transmission at 1.06 and 1.27 μm could be diagnostic of a post-runaway O2-dominated atmosphere from massive H-escape. We find that for these false positive scenarios, CO at 2.35 μm, CO2 at 2.0 and 4.3 μm, and O4 at 1.27 μm are all stronger features in transmission than O2/O3 and could be detected with S/Ns ≳ 3 for an Earth-size planet orbiting a nearby M dwarf star with as few as 10 transits, assuming photon-limited noise. O4 bands could also be sought in UV/VIS/NIR reflected light (at 0.345, 0.36, 0.38, 0.445, 0.475, 0.53, 0.57, 0.63, 1.06, and 1.27 μm) by a next generation direct-imaging telescope such as LUVOIR/HDST or HabEx and would indicate an oxygen atmosphere too massive to be biologically produced.

O2 and O3 have been long considered the most robust individual biosignature gases in a planetary atmosphere, yet multiple mechanisms that may produce them in the absence of life have been described. However, these abiotic planetary mechanisms modify the environment in potentially identifiable ways. Here we briefly discuss two of the most detectable spectral discriminants for abiotic O2/O3: CO and O4. We produce the first explicit self-consistent simulations of these spectral discriminants as they may be seen by JWST. If JWST-NIRISS and/or NIRSpec observe CO (2.35, 4.6 um) in conjunction with CO2 (1.6, 2.0, 4.3 um) in the transmission spectrum of a terrestrial planet it could indicate robust CO2 photolysis and suggest that a future detection of O2 or O3 might not be biogenic. Strong O4 bands seen in transmission at 1.06 and 1.27 um could be diagnostic of a post-runaway O2-dominated atmosphere from massive H-escape. We find that for these false positive scenarios, CO at 2.35 um, CO2 at 2.0 and 4.3 um, and O4 at 1.27 um are all stronger features in transmission than O2/O3 and could be detected with SNRs $\gtrsim$ 3 for an Earth-size planet orbiting a nearby M dwarf star with as few as 10 transits, assuming photon-limited noise. O4 bands could also be sought in UV/VIS/NIR reflected light (at 0.345, 0.36, 0.38, 0.445, 0.475, 0.53, 0.57, 0.63, 1.06, and 1.27 um) by a next generation direct-imaging telescope such as LUVOIR/HDST or HabEx and would indicate an oxygen atmosphere too massive to be biologically produced.