Triple oxygen isotope constraints on atmospheric O2 and biological productivity during the mid-Proterozoic.

Reconstructing the history of biological productivity and atmospheric oxygen partial pressure (pO2) is a fundamental goal of geobiology. Recently, the mass-independent fractionation of oxygen isotopes (O-MIF) has been used as a tool for estimating pO2 and productivity during the Proterozoic. O-MIF, reported as Δ'17O, is produced during the formation of ozone and destroyed by isotopic exchange with water by biological and chemical processes. Atmospheric O-MIF can be preserved in the geologic record when pyrite (FeS2) is oxidized during weathering, and the sulfur is redeposited as sulfate. Here, sedimentary sulfates from the ∼1.4-Ga Sibley Formation are reanalyzed using a detailed one-dimensional photochemical model that includes physical constraints on air-sea gas exchange. Previous analyses of these data concluded that pO2 at that time was <1% PAL (times the present atmospheric level). Our model shows that the upper limit on pO2 is essentially unconstrained by these data. Indeed, pO2 levels below 0.8% PAL are possible only if atmospheric methane was more abundant than today (so that pCO2 could have been lower) or if the Sibley O-MIF data were diluted by reprocessing before the sulfates were deposited. Our model also shows that, contrary to previous assertions, marine productivity cannot be reliably constrained by the O-MIF data because the exchange of molecular oxygen (O2) between the atmosphere and surface ocean is controlled more by air-sea gas transfer rates than by biological productivity. Improved estimates of pCO2 and/or improved proxies for Δ'17O of atmospheric O2 would allow tighter constraints to be placed on mid-Proterozoic pO2.

Oxidized micrometeorites suggest either high pCO2 or low pN2 during the Neoarchean.

Tomkins et al. [A. G. Tomkins et al., Nature 533, 235-238 (2016)] suggested that iron oxides contained in 2.7-Ga iron micrometeorites can be used to determine the concentration of O2 in the Archean upper atmosphere. Specifically, they argued that the presence of magnetite in these objects implies that O2 must have been near present-day levels (∼21%) within the altitude range where the micrometeorites were melted during entry. Here, we reevaluate their data using a 1D photochemical model. We find that atomic oxygen, O, is the most abundant strong oxidant in the upper atmosphere, rather than O2 But data from shock tube experiments suggest that CO2 itself may also serve as the oxidant, in which case micrometeorite oxidation really constrains the CO2/N2 ratio, not the total oxidant abundance. For an atmosphere containing 0.8 bar of N2, like today, the lower limit on the CO2 mixing ratio is ∼0.23. This would produce a mean surface temperature of ∼300 K at 2.7 Ga, which may be too high, given evidence for glaciation at roughly this time. If pN2 was half the present value, and warming by other greenhouse gases like methane was not a major factor, the mean surface temperature would drop to ∼291 K, consistent with glaciation. This suggests that surface pressure in the Neoarchean may need to have been lower-closer to 0.6 bar-for CO2 to have oxidized the micrometeorites. Ultimately, iron micrometeorites may be an indicator for ancient atmospheric CO2 and surface pressure; and could help resolve discrepancies between climate models and existing CO2 proxies such as paleosols.

Nitrous oxide from chemodenitrification: A possible missing link in the Proterozoic greenhouse and the evolution of aerobic respiration.

The potent greenhouse gas nitrous oxide (N2 O) may have been an important constituent of Earth's atmosphere during Proterozoic (~2.5-0.5 Ga). Here, we tested the hypothesis that chemodenitrification, the rapid reduction of nitric oxide by ferrous iron, would have enhanced the flux of N2 O from ferruginous Proterozoic seas. We empirically derived a rate law, d N 2 O d t = 7.2 × 10 - 5 [ Fe 2 + ] 0.3 [ NO ] 1 , and measured an isotopic site preference of +16‰ for the reaction. Using this empirical rate law, and integrating across an oceanwide oxycline, we found that low nM NO and µM-low mM Fe2+ concentrations could have sustained a sea-air flux of 100-200 Tg N2 O-N year-1 , if N2 fixation rates were near-modern and all fixed N2 was emitted as N2 O. A 1D photochemical model was used to obtain steady-state atmospheric N2 O concentrations as a function of sea-air N2 O flux across the wide range of possible pO2 values (0.001-1 PAL). At 100-200 Tg N2 O-N year-1 and >0.1 PAL O2 , this model yielded low-ppmv N2 O, which would produce several degrees of greenhouse warming at 1.6 ppmv CH4 and 320 ppmv CO2 . These results suggest that enhanced N2 O production in ferruginous seawater via a previously unconsidered chemodenitrification pathway may have helped to fill a Proterozoic "greenhouse gap," reconciling an ice-free Mesoproterozoic Earth with a less luminous early Sun. A particularly notable result was that high N2 O fluxes at intermediate O2 concentrations (0.01-0.1 PAL) would have enhanced ozone screening of solar UV radiation. Due to rapid photolysis in the absence of an ozone shield, N2 O is unlikely to have been an important greenhouse gas if Mesoproterozoic O2 was 0.001 PAL. At low O2 , N2 O might have played a more important role as life's primary terminal electron acceptor during the transition from an anoxic to oxic surface Earth, and correspondingly, from anaerobic to aerobic metabolisms.

Could Cirrus Clouds Have Warmed Early Mars?

The presence of the ancient valley networks on Mars indicates that the climate at 3.8 Ga was warm enough to allow substantial liquid water to flow on the martian surface for extended periods of time. However, the mechanism for producing this warming continues to be debated. One hypothesis is that Mars could have been kept warm by global cirrus cloud decks in a CO2-H2O atmosphere containing at least 0.25 bar of CO2 (Urata and Toon, 2013). Initial warming from some other process, e.g., impacts, would be required to make this model work. Those results were generated using the CAM 3-D global climate model. Here, we use a single-column radiative-convective climate model to further investigate the cirrus cloud warming hypothesis. Our calculations indicate that cirrus cloud decks could have produced global mean surface temperatures above freezing, but only if cirrus cloud cover approaches ~75 - 100% and if other cloud properties (e.g., height, optical depth, particle size) are chosen favorably. However, at more realistic cirrus cloud fractions, or if cloud parameters are not optimal, cirrus clouds do not provide the necessary warming, suggesting that other greenhouse mechanisms are needed.

LIMIT CYCLES CAN REDUCE THE WIDTH OF THE HABITABLE ZONE.

The liquid water habitable zone (HZ) describes the orbital distance at which a terrestrial planet can maintain above-freezing conditions through regulation by the carbonate-silicate cycle. Recent calculations have suggested that planets in the outer regions of the HZ cannot maintain stable, warm climates, but rather should oscillate between long, globally glaciated states and shorter periods of climatic warmth. Such conditions, similar to "Snowball Earth" episodes experienced on Earth, would be inimical to the development of complex land life, including intelligent life. Here, we build on previous studies with an updated energy balance climate model to calculate this "limit cycle" region of the HZ where such cycling would occur. We argue that an abiotic Earth would have a greater CO2 partial pressure than today because plants and other biota help to enhance the storage of CO2 in soil. When we tune our abiotic model accordingly, we find that limit cycles can occur but that previous calculations have overestimated their importance. For G stars like the Sun, limit cycles occur only for planets with CO2 outgassing rates less than that on modern Earth. For K- and M-star planets, limit cycles should not occur; however, M-star planets may be inhospitable to life for other reasons. Planets orbiting late G-type and early K-type stars retain the greatest potential for maintaining warm, stable conditions. Our results suggest that host star type, planetary volcanic activity, and seafloor weathering are all important factors in determining whether planets will be prone to limit cycling.

Can increased atmospheric CO2 levels trigger a runaway greenhouse?

Recent one-dimensional (globally averaged) climate model calculations by Goldblatt et al. (2013) suggest that increased atmospheric CO(2) could conceivably trigger a runaway greenhouse on present Earth if CO(2) concentrations were approximately 100 times higher than they are today. The new prediction runs contrary to previous calculations by Kasting and Ackerman (1986), which indicated that CO(2) increases could not trigger a runaway, even at Venus-like CO(2) concentrations. Goldblatt et al. argued that this different behavior is a consequence of updated absorption coefficients for H(2)O that make a runaway more likely. Here, we use a 1-D climate model with similar, up-to-date absorption coefficients, but employ a different methodology, to show that the older result is probably still valid, although our model nearly runs away at ∼12 preindustrial atmospheric levels of CO(2) when we use the most alarmist assumptions possible. However, we argue that Earth's real climate is probably stable given more realistic assumptions, although 3-D climate models will be required to verify this result. Potential CO(2) increases from fossil fuel burning are somewhat smaller than this, 10-fold or less, but such increases could still cause sufficient warming to make much of the planet uninhabitable by humans.

Remote life-detection criteria, habitable zone boundaries, and the frequency of Earth-like planets around M and late K stars.

The habitable zone (HZ) around a star is typically defined as the region where a rocky planet can maintain liquid water on its surface. That definition is appropriate, because this allows for the possibility that carbon-based, photosynthetic life exists on the planet in sufficient abundance to modify the planet's atmosphere in a way that might be remotely detected. Exactly what conditions are needed, however, to maintain liquid water remains a topic for debate. In the past, modelers have restricted themselves to water-rich planets with CO2 and H2O as the only important greenhouse gases. More recently, some researchers have suggested broadening the definition to include arid, "Dune" planets on the inner edge and planets with captured H2 atmospheres on the outer edge, thereby greatly increasing the HZ width. Such planets could exist, but we demonstrate that an inner edge limit of 0.59 AU or less is physically unrealistic. We further argue that conservative HZ definitions should be used for designing future space-based telescopes, but that optimistic definitions may be useful in interpreting the data from such missions. In terms of effective solar flux, S(eff), the recently recalculated HZ boundaries are: recent Venus--1.78; runaway greenhouse--1.04; moist greenhouse--1.01; maximum greenhouse--0.35; and early Mars--0.32. Based on a combination of different HZ definitions, the frequency of potentially Earth-like planets around late K and M stars observed by Kepler is in the range of 0.4-0.5.

Atmospheric production of glycolaldehyde under hazy prebiotic conditions.

The early Earth's atmosphere, with extremely low levels of molecular oxygen and an appreciable abiotic flux of methane, could have been a source of organic compounds necessary for prebiotic chemistry. Here, we investigate the formation of a key RNA precursor, glycolaldehyde (2-hydroxyacetaldehyde, or GA) using a 1-dimensional photochemical model. Maximum atmospheric production of GA occurs when the CH4:CO2 ratio is close to 0.02. The total atmospheric production rate of GA remains small, only 1 × 10(7) mol yr(-1). Somewhat greater amounts of GA production, up to 2 × 10(8) mol yr(-1), could have been provided by the formose reaction or by direct delivery from space. Even with these additional production mechanisms, open ocean GA concentrations would have remained at or below ~1 µM, much smaller than the 1-2 M concentrations required for prebiotic synthesis routes like those proposed by Powner et al. (Nature 459:239-242, 2009). Additional production or concentration mechanisms for GA, or alternative formation mechanisms for RNA, are needed, if this was indeed how life originated on the early Earth.

Tidal Venuses: triggering a climate catastrophe via tidal heating.

Traditionally, stellar radiation has been the only heat source considered capable of determining global climate on long timescales. Here, we show that terrestrial exoplanets orbiting low-mass stars may be tidally heated at high-enough levels to induce a runaway greenhouse for a long-enough duration for all the hydrogen to escape. Without hydrogen, the planet no longer has water and cannot support life. We call these planets "Tidal Venuses" and the phenomenon a "tidal greenhouse." Tidal effects also circularize the orbit, which decreases tidal heating. Hence, some planets may form with large eccentricity, with its accompanying large tidal heating, and lose their water, but eventually settle into nearly circular orbits (i.e., with negligible tidal heating) in the habitable zone (HZ). However, these planets are not habitable, as past tidal heating desiccated them, and hence should not be ranked highly for detailed follow-up observations aimed at detecting biosignatures. We simulated the evolution of hypothetical planetary systems in a quasi-continuous parameter distribution and found that we could constrain the history of the system by statistical arguments. Planets orbiting stars with masses<0.3 MSun may be in danger of desiccation via tidal heating. We have applied these concepts to Gl 667C c, a ∼4.5 MEarth planet orbiting a 0.3 MSun star at 0.12 AU. We found that it probably did not lose its water via tidal heating, as orbital stability is unlikely for the high eccentricities required for the tidal greenhouse. As the inner edge of the HZ is defined by the onset of a runaway or moist greenhouse powered by radiation, our results represent a fundamental revision to the HZ for noncircular orbits. In the appendices we review (a) the moist and runaway greenhouses, (b) hydrogen escape, (c) stellar mass-radius and mass-luminosity relations, (d) terrestrial planet mass-radius relations, and (e) linear tidal theories.

The carbonate-silicate cycle and CO2/climate feedbacks on tidally locked terrestrial planets.

Atmospheric gaseous constituents play an important role in determining the surface temperatures and habitability of a planet. Using a global climate model and a parameterization of the carbonate-silicate cycle, we explored the effect of the location of the substellar point on the atmospheric CO(2) concentration and temperatures of a tidally locked terrestrial planet, using the present Earth continental distribution as an example. We found that the substellar point's location relative to the continents is an important factor in determining weathering and the equilibrium atmospheric CO(2) level. Placing the substellar point over the Atlantic Ocean results in an atmospheric CO(2) concentration of 7 ppmv and a global mean surface air temperature of 247 K, making ∼30% of the planet's surface habitable, whereas placing it over the Pacific Ocean results in a CO(2) concentration of 60,311 ppmv and a global temperature of 282 K, making ∼55% of the surface habitable.

Using biogenic sulfur gases as remotely detectable biosignatures on anoxic planets.

We used one-dimensional photochemical and radiative transfer models to study the potential of organic sulfur compounds (CS(2), OCS, CH(3)SH, CH(3)SCH(3), and CH(3)S(2)CH(3)) to act as remotely detectable biosignatures in anoxic exoplanetary atmospheres. Concentrations of organic sulfur gases were predicted for various biogenic sulfur fluxes into anoxic atmospheres and were found to increase with decreasing UV fluxes. Dimethyl sulfide (CH(3)SCH(3), or DMS) and dimethyl disulfide (CH(3)S(2)CH(3), or DMDS) concentrations could increase to remotely detectable levels, but only in cases of extremely low UV fluxes, which may occur in the habitable zone of an inactive M dwarf. The most detectable feature of organic sulfur gases is an indirect one that results from an increase in ethane (C(2)H(6)) over that which would be predicted based on the planet's methane (CH(4)) concentration. Thus, a characterization mission could detect these organic sulfur gases-and therefore the life that produces them-if it could sufficiently quantify the ethane and methane in the exoplanet's atmosphere.

Availability of O(2) and H(2)O(2) on pre-photosynthetic Earth.

Old arguments that free O(2) must have been available at Earth's surface prior to the origin of photosynthesis have been revived by a new study that shows that aerobic respiration can occur at dissolved oxygen concentrations much lower than had previously been thought, perhaps as low as 0.05 nM, which corresponds to a partial pressure for O(2) of about 4 × 10(-8) bar. We used numerical models to study whether such O(2) concentrations might have been provided by atmospheric photochemistry. Results show that disproportionation of H(2)O(2) near the surface might have yielded enough O(2) to satisfy this constraint. Alternatively, poleward transport of O(2) from the equatorial stratosphere into the polar night region, followed by downward transport in the polar vortex, may have brought O(2) directly to the surface. Thus, our calculations indicate that this "early respiration" hypothesis might be physically reasonable.

A revised, hazy methane greenhouse for the Archean Earth.

Geological and biological evidence suggests that Earth was warm during most of its early history, despite the fainter young Sun. Upper bounds on the atmospheric CO2 concentration in the Late Archean/Paleoproterozoic (2.8-2.2 Ga) from paleosol data suggest that additional greenhouse gases must have been present. Methanogenic bacteria, which were arguably extant at that time, may have contributed to a high concentration of atmospheric CH4, and previous calculations had indicated that a CH4-CO2-H2O greenhouse could have produced warm Late Archean surface temperatures while still satisfying the paleosol constraints on pCO2. Here, we revisit this conclusion. Correction of an error in the CH4 absorption coefficients, combined with the predicted early onset of climatically cooling organic haze, suggest that the amount of greenhouse warming by CH4 was more limited and that pCO2 must therefore have been 0.03 bar, at or above the upper bound of the value obtained from paleosols. Enough warming from CH4 remained in the Archean, however, to explain why Earth's climate cooled and became glacial when atmospheric O2 levels rose in the Paleoproterozoic. Our new model also shows that greenhouse warming by higher hydrocarbon gases, especially ethane (C2H6), may have helped to keep the Late Archean Earth warm.