Rapid timescale for an oxic transition during the Great Oxidation Event and the instability of low atmospheric O2.

The Great Oxidation Event (GOE), arguably the most important event to occur on Earth since the origin of life, marks the time when an oxygen-rich atmosphere first appeared. However, it is not known whether the change was abrupt and permanent or fitful and drawn out over tens or hundreds of millions of years. Here, we developed a one-dimensional time-dependent photochemical model to resolve time-dependent behavior of the chemically unstable transitional atmosphere as it responded to changes in biogenic forcing. When forced with step-wise changes in biogenic fluxes, transitions between anoxic and oxic atmospheres take between only 102 and 105 y. Results also suggest that O2 between [Formula: see text] and [Formula: see text] mixing ratio is unstable to plausible atmospheric perturbations. For example, when atmospheres with these O2 concentrations experience fractional variations in the surface CH4 flux comparable to those caused by modern Milankovich cycling, oxygen fluctuates between anoxic ([Formula: see text]) and oxic ([Formula: see text]) mixing ratios. Overall, our simulations are consistent with possible geologic evidence of unstable atmospheric O2, after initial oxygenation, which could occasionally collapse from changes in biospheric or volcanic fluxes. Additionally, modeling favors mid-Proterozoic O2 exceeding [Formula: see text] to [Formula: see text] mixing ratio; otherwise, O2 would periodically fall below [Formula: see text] mixing ratio, which would be inconsistent with post-GOE absence of sulfur isotope mass-independent fractionation.

Massive perturbations to atmospheric sulfur in the aftermath of the Chicxulub impact.

SignificanceSulfur isotopes confirm a key role for atmospheric sulfur gases in climatic cooling, mass extinction, and the demise of dinosaurs and other global biota after the Chicxulub bolide impact at the Cretaceous-Paleogene boundary. The sulfur isotope anomalies are confined to beds containing ejecta and, in the immediately overlying sediments, are temporally unrelated to known episodes of volcanism that also bracket this event, further addressing the controversial role of the Deccan Traps in the extinction.

Onset of the aerobic nitrogen cycle during the Great Oxidation Event.

The rise of oxygen on the early Earth (about 2.4 billion years ago) caused a reorganization of marine nutrient cycles, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope (15N/14N) values from approximately 2.31-billion-year-old shales of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event). Our data fill a gap of about 400 million years in the temporal 15N/14N record and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton.

The Great Oxidation Event preceded a Paleoproterozoic "snowball Earth".

The inability to resolve the exact temporal relationship between two pivotal events in Earth history, the Paleoproterozoic Great Oxidation Event (GOE) and the first "snowball Earth" global glaciation, has precluded assessing causality between changing atmospheric composition and ancient climate change. Here we present temporally resolved quadruple sulfur isotope measurements (δ34S, ∆33S, and ∆36S) from the Paleoproterozoic Seidorechka and Polisarka Sedimentary Formations on the Fennoscandian Shield, northwest Russia, that address this issue. Sulfides in the former preserve evidence of mass-independent fractionation of sulfur isotopes (S-MIF) falling within uncertainty of the Archean reference array with a ∆36S/∆33S slope of -1.8 and have small negative ∆33S values, whereas in the latter mass-dependent fractionation of sulfur isotopes (S-MDF) is evident, with a ∆36S/∆33S slope of -8.8. These trends, combined with geochronological constraints, place the S-MIF/S-MDF transition, the key indicator of the GOE, between 2,501.5 ± 1.7 Ma and 2,434 ± 6.6 Ma. These are the tightest temporal and stratigraphic constraints yet for the S-MIF/S-MDF transition and show that its timing in Fennoscandia is consistent with the S-MIF/S-MDF transition in North America and South Africa. Further, the glacigenic part of the Polisarka Formation occurs 60 m above the sedimentary succession containing S-MDF signals. Hence, our findings confirm unambiguously that the S-MIF/S-MDF transition preceded the Paleoproterozoic snowball Earth. Resolution of this temporal relationship constrains cause-and-effect drivers of Earth's oxygenation, specifically ruling out conceptual models in which global glaciation precedes or causes the evolution of oxygenic photosynthesis.

Spatial Variability of Microbial Communities and Salt Distributions Across a Latitudinal Aridity Gradient in the Atacama Desert.

Over the past 150 million years, the Chilean Atacama Desert has been transformed into one of the most inhospitable landscapes by geophysical changes, which makes it an ideal Mars analog that has been explored for decades. However, a heavy rainfall that occurred in the Atacama in 2017 provides a unique opportunity to study the response of resident extremophiles to rapid environmental change associated with excessive water and salt shock. Here we combine mineral/salt composition measurements, amendment cell culture experiments, and next-generation sequencing analyses to study the variations in salts and microbial communities along a latitudinal aridity gradient of the Atacama Desert. In addition, we examine the reshuffling of Atacama microbiomes after the rainfall event. Analysis of microbial community composition revealed that soils within the southern arid desert were consistently dominated by Actinobacteria, Chloroflexi, Proteobacteria, Firmicutes, Bacteroidetes, Gemmatimonadetes, Planctomycetes, and Acidobacteria, and Verrucomicrobia. Intriguingly, the hyperarid microbial consortia exhibited a similar pattern to the more southern desert. Salts at the shallow subsurface were dissolved and leached down to a deeper layer, challenging indigenous microorganisms with the increasing osmotic stress. Microbial viability was found to change with aridity and rainfall events. This study sheds light on the structure of xerotolerant, halotolerant, and radioresistant microbiomes from the hyperarid northern desert to the less arid southern transition region, as well as their response to changes in water availability.

Biological regulation of atmospheric chemistry en route to planetary oxygenation.

Emerging evidence suggests that atmospheric oxygen may have varied before rising irreversibly ∼2.4 billion years ago, during the Great Oxidation Event (GOE). Significantly, however, pre-GOE atmospheric aberrations toward more reducing conditions-featuring a methane-derived organic-haze-have recently been suggested, yet their occurrence, causes, and significance remain underexplored. To examine the role of haze formation in Earth's history, we targeted an episode of inferred haze development. Our redox-controlled (Fe-speciation) carbon- and sulfur-isotope record reveals sustained systematic stratigraphic covariance, precluding nonatmospheric explanations. Photochemical models corroborate this inference, showing Δ36S/Δ33S ratios are sensitive to the presence of haze. Exploiting existing age constraints, we estimate that organic haze developed rapidly, stabilizing within ∼0.3 ± 0.1 million years (Myr), and persisted for upward of ∼1.4 ± 0.4 Myr. Given these temporal constraints, and the elevated atmospheric CO2 concentrations in the Archean, the sustained methane fluxes necessary for haze formation can only be reconciled with a biological source. Correlative δ13COrg and total organic carbon measurements support the interpretation that atmospheric haze was a transient response of the biosphere to increased nutrient availability, with methane fluxes controlled by the relative availability of organic carbon and sulfate. Elevated atmospheric methane concentrations during haze episodes would have expedited planetary hydrogen loss, with a single episode of haze development providing up to 2.6-18 × 1018 moles of O2 equivalents to the Earth system. Our findings suggest the Neoarchean likely represented a unique state of the Earth system where haze development played a pivotal role in planetary oxidation, hastening the contingent biological innovations that followed.

Triple oxygen isotope analysis of nitrate using isotope exchange cavity ringdown laser spectroscopy.

RATIONALE: Triple oxygen isotopes (16 O/17 O/18 O) in nitrate are a valuable tool to ascertain the pathways of nitrate formation in the atmosphere and the fate of nitrate in ecosystems. Here we present a new method for determining Δ17 O values in nitrates, based on nitrate-water isotope equilibration (IE) and subsequent isotopic analysis of water using cavity ringdown laser spectroscopy (CRDS). METHODS: Nitrate oxygen (O-NO3 - ) is equilibrated with water oxygen (O-H2 O) at low pH and 80°C. Subsequently, the δ17 O and δ18 O values of equilibrated water are determined by CRDS, scaled to V-SMOW and V-SLAP and calibrated against nitrate standards (USGS-34, USGS-35 and IAEA-NO3). We provide isotopic measurements of synthetic and natural nitrates and a direct inter-lab comparison with the classic method of thermal-decomposition of nitrate followed by isotope ratio mass spectrometry of O2 (TD-IRMS). RESULTS: For synthetic NaNO3 , the precision (1SD) of the IE-CRDS method is 0.8‰ for δ17 O values, 1.7‰ for δ18 O values and 0.2‰ for Δ17 O values when using an O-NO3 - /O-H2 O ratio greater than 0.0114 ± 0.0001 (e.g. 12 µmol of NO3 - in 50 µL of acid solution). For natural samples, after purification of nitrates by column chemistry and reprecipitation as AgNO3 , the precision is better than 1.8‰ for δ17 O values, 3.2‰ for δ18 O values and 1‰ for Δ17 O values. IE-CRDS and TD-IRMS yield Δ17 O values within the analytical errors of the two methods. CONCLUSIONS: The IE-CRDS method for determining Δ17 O values in nitrates utilizes a user-friendly and relatively cheaper benchtop analytical instrument, representing an alternative to IRMS-based methods for certain applications.

Nitrogen Cycling and Biosignatures in a Hyperarid Mars Analog Environment.

The hyperarid Atacama Desert is a unique Mars-analog environment with a large near-surface soil nitrate reservoir due to the lack of rainfall leaching for millennia. We investigated nitrogen (N) cycling and organic matter dynamics in this nitrate-rich terrestrial environment by analyzing the concentrations and isotopic compositions of nitrate, organic C, and organic N, coupled with microbial pathway-enzyme inferences, across a naturally occurring rainfall gradient. Nitrate deposits in sites with an annual precipitation of <10 mm carry atmospheric δ15N, δ18O, and Δ17O signatures, while these values are overprinted by biological cycling in sites with >15 mm annual precipitation. Metagenomic analyses suggest that the Atacama Desert harbors a unique biological nitrogen cycle driven by nitrifier denitrification, nitric oxide dioxygenase-driven alternative nitrification, and organic N loss pathways. Nitrate assimilation is the only nitrate consumption pathway available in the driest sites, although some hyperarid sites also support organisms with ammonia lyase- and nitric oxide synthase-driven organic N loss. Nitrifier denitrification is enhanced in the "transition zone" desert environments, which are generally hyperarid but see occasional large rainfall events, and shifts to nitric oxide dioxygenase-driven alternative nitrifications in wetter arid sites. Since extremophilic microorganisms tend to exploit all reachable nutrients, both N and O isotope fractionations during N transformations are reduced. These results suggest that N cycling on the more recent dry Mars might be dominated by nitrate assimilation that cycles atmospheric nitrate and exchanges water O during intermittent wetting, resulting stable isotope biosignatures could shift away from martian atmospheric nitrate endmember. Early wetter Mars could nurture putative life that metabolized nitrate with traceable paleoenvironmental isotopic markers similar to microbial denitrification and nitrification stored in deep subsurface.

Unraveling biogeochemical phosphorus dynamics in hyperarid Mars-analogue soils using stable oxygen isotopes in phosphate.

With annual precipitation less than 20 mm and extreme UV intensity, the Atacama Desert in northern Chile has long been utilized as an analogue for recent Mars. In these hyperarid environments, water and biomass are extremely limited, and thus, it becomes difficult to generate a full picture of biogeochemical phosphate-water dynamics. To address this problem, we sampled soils from five Atacama study sites and conducted three main analyses-stable oxygen isotopes in phosphate, enzyme pathway predictions, and cell culture experiments. We found that high sedimentation rates decrease the relative size of the organic phosphorus pool, which appears to hinder extremophiles. Phosphoenzyme and pathway prediction analyses imply that inorganic pyrophosphatase is the most likely catalytic agent to cycle P in these environments, and this process will rapidly overtake other P utilization strategies. In these soils, the biogenic δ18 O signatures of the soil phosphate (δ18 OPO4 ) can slowly overprint lithogenic δ18 OPO4 values over a timescale of tens to hundreds of millions of years when annual precipitation is more than 10 mm. The δ18 OPO4 of calcium-bound phosphate minerals seems to preserve the δ18 O signature of the water used for biogeochemical P cycling, pointing toward sporadic rainfall and gypsum hydration water as key moisture sources. Where precipitation is less than 2 mm, biological cycling is restricted and bedrock δ18 OPO4 values are preserved. This study demonstrates the utility of δ18 OPO4 values as indicative of biogeochemical cycling and hydrodynamics in an extremely dry Mars-analogue environment.

Nitrates as a Potential N Supply for Microbial Ecosystems in a Hyperarid Mars Analog System.

Nitrate is common in Mars sediments owing to long-term atmospheric photolysis, oxidation, and potentially, impact shock heating. The Atacama Desert in Chile, which is the driest region on Earth and rich in nitrate deposits, is used as a Mars analog in this study to explore the potential effects of high nitrate levels on growth of extremophilic ecosystems. Seven study sites sampled across an aridity gradient in the Atacama Desert were categorized into 3 clusters-hyperarid, middle, and arid sites-as defined by essential soil physical and chemical properties. Intriguingly, the distribution of nitrate concentrations in the shallow subsurface suggests that the buildup of nitrate is not solely controlled by precipitation. Correlations of nitrate with SiO2/Al2O3 and grain sizes suggest that sedimentation rates may also be important in controlling nitrate distribution. At arid sites receiving more than 10 mm/yr precipitation, rainfall shows a stronger impact on biomass than nitrate does. However, high nitrate to organic carbon ratios are generally beneficial to N assimilation, as evidenced both by soil geochemistry and enriched culturing experiments. This study suggests that even in the absence of precipitation, nitrate levels on a more recent, hyperarid Mars could be sufficiently high to benefit potentially extant Martian microorganisms.

Evaluation of the Tindouf Basin Region in Southern Morocco as an Analogue Site for Soil Geochemistry on Noachian Mars.

Locations on Earth that provide insights into processes that may be occurring or may have occurred throughout martian history are often broadly deemed "Mars analog environments." As no single locale can precisely represent a past or present martian environment, it is important to focus on characterization of terrestrial processes that produce analogous features to those observed in specific regions of Mars or, if possible, specific time periods during martian history. Here, we report on the preservation of ionic species in soil samples collected from the Tindouf region of Morocco and compare them with the McMurdo Dry Valleys of Antarctica, the Atacama Desert in Chile, the martian meteorite EETA79001, and the in situ Mars analyses from the Phoenix Wet Chemistry Laboratory (WCL). The Moroccan samples show the greatest similarity with those from Victoria Valley, Beacon Valley, and the Atacama, while being consistently depleted compared to University Valley and enriched compared to Taylor Valley. The NO3/Cl ratios are most similar to Victoria Valley and Atacama, while the SO4/Cl ratios are similar to those from Beacon Valley, Victoria Valley, and the Atacama. While perchlorate concentrations in the Moroccan samples are typically lower than those found in samples of other analog sites, conditions in the region are sufficiently arid to retain oxychlorines at detectable levels. Our results suggest that the Tindouf Basin in Morocco can serve as a suitable analogue for the soil geochemistry and subsequent aridification of the Noachian epoch on Mars.

Long-Term Planetary Habitability and the Carbonate-Silicate Cycle.

The potential habitability of an exoplanet is traditionally assessed by determining whether its orbit falls within the circumstellar "habitable zone" of its star, defined as the distance at which water could be liquid on the surface of a planet (Kopparapu et al., 2013 ). Traditionally, these limits are determined by radiative-convective climate models, which are used to predict surface temperatures at user-specified levels of greenhouse gases. This approach ignores the vital question of the (bio)geochemical plausibility of the proposed chemical abundances. Carbon dioxide is the most important greenhouse gas in Earth's atmosphere in terms of regulating planetary temperature, with the long-term concentration controlled by the balance between volcanic outgassing and the sequestration of CO2 via chemical weathering and sedimentation, as modulated by ocean chemistry, circulation, and biological (microbial) productivity. We developed a model that incorporates key aspects of Earth's short- and long-term biogeochemical carbon cycle to explore the potential changes in the CO2 greenhouse due to variance in planet size and stellar insolation. We find that proposed changes in global topography, tectonics, and the hydrological cycle on larger planets result in proportionally greater surface temperatures for a given incident flux. For planets between 0.5 and 2 R⊕, the effect of these changes results in average global surface temperature deviations of up to 20 K, which suggests that these relationships must be considered in future studies of planetary habitability. Key Words: Planets-Atmospheres-Carbon dioxide-Biogeochemistry. Astrobiology 18, 469-480.

Habitable zone lifetimes of exoplanets around main sequence stars.

The potential habitability of newly discovered exoplanets is initially assessed by determining whether their orbits fall within the circumstellar habitable zone of their star. However, the habitable zone (HZ) is not static in time or space, and its boundaries migrate outward at a rate proportional to the increase in luminosity of a star undergoing stellar evolution, possibly including or excluding planets over the course of the star's main sequence lifetime. We describe the time that a planet spends within the HZ as its "habitable zone lifetime." The HZ lifetime of a planet has strong astrobiological implications and is especially important when considering the evolution of complex life, which is likely to require a longer residence time within the HZ. Here, we present results from a simple model built to investigate the evolution of the "classic" HZ over time, while also providing estimates for the evolution of stellar luminosity over time in order to develop a "hybrid" HZ model. These models return estimates for the HZ lifetimes of Earth and 7 confirmed HZ exoplanets and 27 unconfirmed Kepler candidates. The HZ lifetime for Earth ranges between 6.29 and 7.79×109 years (Gyr). The 7 exoplanets fall in a range between ∼1 and 54.72 Gyr, while the 27 Kepler candidate planets' HZ lifetimes range between 0.43 and 18.8 Gyr. Our results show that exoplanet HD 85512b is no longer within the HZ, assuming it has an Earth analog atmosphere. The HZ lifetime should be considered in future models of planetary habitability as setting an upper limit on the lifetime of any potential exoplanetary biosphere, and also for identifying planets of high astrobiological potential for continued observational or modeling campaigns.

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.