Present Atmospheric Level Research Articles

Insights from a dynamical system approach into the history of atmospheric oxygenation

Atmospheric oxygen levels are traditionally viewed to have been relatively stable throughout Earth’s history with several-step increases. Emerging evidence, however, suggests extremely dynamic atmospheric oxygen levels through large swaths of Earth’s history. Here, we provide a new perspective on atmospheric oxygen evolution using a dynamical analysis to explore the relative importance of previously proposed feedbacks on the global oxygen and carbon cycles. Our results from a stochastic analysis of oxygen mass balance in this framework suggest there are multiple steady states for atmospheric oxygen, but only three stable states. One stable state under anoxic conditions (<10−5 present atmospheric level (PAL)), one at low (~10−3to 10−2 PAL), and one near modern value atmospheric oxygen levels. Our findings also suggest two unstable states (tipping points) for atmospheric oxygen: one around 10−5 and another one around 10−1 PAL.

Nitrogen isotope gradient on continental margins during the late Paleoproterozoic

The late Paleoproterozoic was a key period in the evolution of Earth’s surface environments and life. It is generally accepted that during the 2.43–2.06 Ga Great Oxidation Episode, the atmospheric oxygen level rose to an intermediate state (0.1% to 10% of the present atmospheric level) and the chemical composition of the oceans changed significantly. The paleontological record indicates that eukaryotes appeared during the late Paleoproterozoic. Nitrogen, an essential nutrient for life, is thought to have been one of the key factors in eukaryote evolution. However, nitrogen bioavailability and spatial heterogeneity in nitrogen cycle in the late Paleoproterozoic oceans remain controversial. Here, we examine carbon and nitrogen cycling in the late Paleoproterozoic ocean, via analysis of redox-sensitive element contents and organic carbon and nitrogen isotope compositions of black shales of the ca. 1.9 Ga Nuvilic Formation of the Povungnituk Group, Cape Smith Belt, Canada. Two diamond drill-holes (DDHs) 718–3333 (∼50 m-long) and 4G8069 (∼90 m-long) investigated in this study contain turbiditic greywackes and black shales deposited on the northern margin of the Archean Superior craton below the storm wave-base. Sedimentary rocks of DDH 4G8069 might have been deposited closer to the continental source area, as indicated by sandstone abundance, than those of DDH 718–3333. Redox-sensitive element (V, U, and Mo) contents in black shales of DDH 4G8069 are low and show positive correlation with Al contents, whereas those of DDH 718–3333 are irregularly elevated. Fe/Al ratios of DDH 718–3333 are low, which likely reflect Fe loss from sediments under anoxic water-column conditions. Depositional environment is inferred to be above and below the redoxcline for DDHs 4G8069 and 718–3333, respectively. Organic carbon isotope values of DDH 718–3333 are approximately 1.7‰ lighter than those of DDH 4G8069, which might reflect methane cycling at the redoxcline. Nitrogen isotope values are positive (> +3‰) for all the black shale samples, corresponding to aerobic nitrogen cycling and presence of bioavailable nitrate on the northern margin of the Superior craton during the late Paleoproterozoic. Furthermore, nitrogen isotope values for DDH 718–3333 are approximately 2‰ heavier than those for DDH 4G8069. The observed isotopic heterogeneity is similar to that in modern oxygen-minimum zones and could represent intense denitrification at the redoxcline. Although no ca. 1.9 Ga microfossils reported to date are considered unambiguously eukaryotic, the aerobic nitrogen cycling inferred for the Nuvilic Formation, as well as for the previously studied Rove, Virginia, and Menihek formations, suggests that nitrogen limitation was unlikely to have inhibited biological evolution during the late Paleoproterozoic, a finding that is consistent with molecular clock studies suggesting that the emergence of eukaryotes occurred during the Paleoproterozoic.

Constraining the oxygen requirements for modern microbial eukaryote diversity.

Eukaryotes originated prior to the establishment of modern marine oxygen (O2) levels. According to the body fossil and lipid biomarker records, modern (crown) microbial eukaryote lineages began diversifying in the ocean no later than ~800 Ma. While it has long been predicted that increasing atmospheric O2 levels facilitated the early diversification of microbial eukaryotes, the O2 levels needed to permit this diversification remain unconstrained. Using time-resolved geochemical parameter and gene sequence information from a model marine oxygen minimum zone spanning a range of dissolved O2 levels and redox states, we show that microbial eukaryote taxonomic richness and phylogenetic diversity remain the same until O2 declines to around 2 to 3% of present atmospheric levels, below which these diversity metrics become significantly reduced. Our observations suggest that increasing O2 would have only directly promoted early crown-eukaryote diversity if atmospheric O2 was below 2 to 3% of modern levels when crown-eukaryotes originated and then later met or surpassed this range as crown-eukaryotes diversified. If atmospheric O2 was already consistently at or above 2 to 3% of modern levels by the time that crown-eukaryotes originated, then the subsequent diversification of modern microbial eukaryotes was not directly driven by atmospheric oxygenation.

Stratospheric dayside-to-nightside circulation drives the 3D ozone distribution on synchronously rotating rocky exoplanets

ABSTRACT Determining the habitability and interpreting future atmospheric observations of exoplanets requires understanding the atmospheric dynamics and chemistry from a 3D perspective. Previous studies have shown significant spatial variability in the ozone layer of synchronously rotating M-dwarf planets, assuming an Earth-like initial atmospheric composition. We simulate Proxima Centauri b in an 11.2-d orbit around its M-type host star using a 3D coupled climate-chemistry model to understand the spatial variability of ozone and identify the mechanism responsible for it. We document a previously unreported connection between the ozone production regions on the photochemically active dayside hemisphere and the nightside devoid of stellar radiation and thus photochemistry. We find that stratospheric dayside-to-nightside overturning circulation can advect ozone-rich air to the nightside. On the nightside, ozone-rich air subsides at the locations of two quasi-stationary Rossby gyres, resulting in an exchange between the stratosphere and troposphere and the accumulation of ozone at the gyre locations. The mechanism drives the ozone distribution for both the present atmospheric level (PAL) and a 0.01 PAL O2 atmosphere. We identify the hemispheric contrast in radiative heating and cooling as the main driver of the stratospheric dayside-to-nightside circulation. An age-of-air experiment shows that the mechanism also impacts other tracer species in the atmosphere (gaseous and non-gaseous phase) as long as chemical lifetimes exceed dynamical lifetimes. These findings, applicable to exoplanets in similar orbital configurations, illustrate the 3D nature of planetary atmospheres and the spatial and temporal variability that we can expect to impact spectroscopic observations of exoplanet atmospheres.

Evolution of iron and oxygen biogeochemical cycles during the Precambrian.

Iron (Fe) is an essential element for life, and its geochemical cycle is intimately linked to the coupled history of life and Earth's environment. The accumulated geologic records indicate that ferruginous waters existed in the Precambrian oceans not only before the first major rise of atmospheric O2 levels (Great Oxidation Event; GOE) during the Paleoproterozoic, but also during the rest of the Proterozoic. However, the interactive evolution of the biogeochemical cycles of O2 and Fe during the Archean-Proterozoic remains ambiguous. Here, we develop a biogeochemical model to investigate the coupled biogeochemical evolution of Fe-O2 -P-C cycles across the GOE. Our model demonstrates that the marine Fe cycle was less sensitive to changes in the production rate of O2 before the GOE (atmospheric pO2 < 10-6 PAL; present atmospheric level). When the P supply rate to the ocean exceeds a certain threshold, the GOE occurs and atmospheric pO2 rises to ~10-3 -10-1 PAL. After the GOE, the marine Fe(II) concentration is highly sensitive to atmospheric pO2 , suggesting that the marine redox landscape during the Proterozoic may have fluctuated between ferruginous conditions and anoxic non-ferruginous conditions with sulfidic water masses around continental margins. At a certain threshold value of atmospheric pO2 of ~0.3% PAL, the primary oxidation pathway of Fe(II) shifts from the activity of Fe(II)-utilizing anoxygenic photoautotrophs in sunlit surface waters to abiotic process in the deep ocean. This is accompanied by a shift in the primary deposition site of Fe(III) hydroxides from the surface ocean to the deep sea, providing a plausible mechanistic explanation for the observed cessation of iron formations during the Proterozoic.

White and green rust chimneys accumulate RNA in a ferruginous chemical garden.

Mechanisms of nucleic acid accumulation were likely critical to life's emergence in the ferruginous oceans of the early Earth. How exactly prebiotic geological settings accumulated nucleic acids from dilute aqueous solutions, is poorly understood. As a possible solution to this concentration problem, we simulated the conditions of prebiotic low-temperature alkaline hydrothermal vents in co-precipitation experiments to investigate the potential of ferruginous chemical gardens to accumulate nucleic acids via sorption. The injection of an alkaline solution into an artificial ferruginous solution under anoxic conditions (O2 < 0.01% of present atmospheric levels) and at ambient temperatures, caused the precipitation of amakinite ("white rust"), which quickly converted to chloride-containing fougerite ("green rust"). RNA was only extractable from the ferruginous solution in the presence of a phosphate buffer, suggesting RNA in solution was bound to Fe2+ ions. During chimney formation, this iron-bound RNA rapidly accumulated in the white and green rust chimney structure from the surrounding ferruginous solution at the fastest rates in the initial white rust phase and correspondingly slower rates in the following green rust phase. This represents a new mechanism for nucleic acid accumulation in the ferruginous oceans of the early Earth, in addition to wet-dry cycles and may have helped to concentrate RNA in a dilute prebiotic ocean.

Proterozoic Acquisition of Archaeal Genes for Extracellular Electron Transfer: A Metabolic Adaptation of Aerobic Ammonia-Oxidizing Bacteria to Oxygen Limitation.

Many aerobic microbes can utilize alternative electron acceptors under oxygen-limited conditions. In some cases, this is mediated by extracellular electron transfer (or EET), wherein electrons are transferred to extracellular oxidants such as iron oxide and manganese oxide minerals. Here, we show that an ammonia-oxidizer previously known to be strictly aerobic, Nitrosomonas communis, may have been able to utilize a poised electrode to maintain metabolic activity in anoxic conditions. The presence and activity of multiheme cytochromes in N. communis further suggest a capacity for EET. Molecular clock analysis shows that the ancestors of β-proteobacterial ammonia oxidizers appeared after Earth's atmospheric oxygenation when the oxygen levels were >10-4pO2 (present atmospheric level [PAL]), consistent with aerobic origins. Equally important, phylogenetic reconciliations of gene and species trees show that the multiheme c-type EET proteins in Nitrosomonas and Nitrosospira lineages were likely acquired by gene transfer from γ-proteobacteria when the oxygen levels were between 0.1 and 1 pO2 (PAL). These results suggest that β-proteobacterial EET evolved during the Proterozoic when oxygen limitation was widespread, but oxidized minerals were abundant.

Extensive sea-floor oxygenation during the early Mesoproterozoic

The Mesoproterozoic ocean was previously proposed to be characterized by low oxygen concentrations that may have resulted in a stasis in eukaryotic evolution. Recent studies reveal several pluses of oxygenation during this period that may have facilitated eukaryote evolution. However, few quantitative constraints on the global oxygenation events have hindered the comprehensive understanding of interactions between eukaryotes and environments. Here we present new molybdenum isotope (δ98/95Mo, simplified as δ98Mo) data coupled with sulfur and carbon isotope compositions and trace element contents from the carbonates and mudstones of the Gaoyuzhuang Formation (ca. 1.60–1.54 Ga) in two-well preserved sections in the North China Craton. The δ98Mo data from the two sections show similar trends in stratigraphic variation, with a prominent positive excursion in the Gaoyuzhuang Member III and peak values reaching up to 2.03‰ and 1.92‰, respectively. We developed a revised isotope mass balance model with high manganese (Mn) (hydr)oxide burial rate due to higher manganese concentration in the Mesoproterozoic oceans. Model calculation suggests that at least more than half of global seafloor (>54%) was covered with oxygenated seawater during the deposition of the Gaoyuzhuang Member III. Our estimation points to a significant oxygenation event in the early Mesoproterozoic with magnitude and extent much higher than previously thought. Further, a simple mass-balance calculation suggests that the atmospheric oxygen level was at least > 4% PAL (present atmospheric level) and likely up to 30% PAL at ca. 1.57 Ga. This oxygenation event, together with other environmental and/or developmental factors, may have facilitated a short and rapid evolution of eukaryotes in the early Mesoproterozoic.

Magnetic Circular Dichroism in Archean Stratospheric Oxygen: Enantiomeric Excess of Amino Acids Produced in Volcanic Plumes.

While there is consensus that Archean atmosphere was anoxic with O2 pressure, p(O2) <10-6 PAL (present atmospheric level) at sea-level, evidence suggests that p(O2) at stratospheric altitudes of 10-50 km was orders of magnitude higher, a result of photodissociation of CO2 by UVC sunlight and incomplete mixing of O2 with other gases. Molecular O2 is paramagnetic due to triplet ground state. Magnetic circular dichroism (MCD) by stratospheric O2 is examined in earth's magnetic field and shows maximum circular polarization │(I+ - I-)│ at altitude of 15-30 km (I+/I- is intensity of left/right circularly polarized light). While (I+ - I-)/(I+ + I-) is small (~10-10), it is an unexplored source of enantiomeric excess (EE) by asymmetric photolysis of amino acid precursors produced in volcanic eruptions. The precursors reside in stratosphere for periods of over a year due to relative absence of vertical transport. Due to negligible thermal gradient across equator, they are trapped in the hemisphere where they are produced, with interhemispheric exchange time of over a year. The precursors diffuse through altitudes of maximum circular polarization before getting hydrolyzed on ground to amino acids. Enantiomeric excess of ~10-12 is calculated for precursors and amino acids. While small, this EE is orders of magnitude higher than predicted (~10-18) by parity violating energy differences (PVED) and could be the seed for growth of biological homochirality. Preferential crystallization (PC) is described as a plausible mechanism for amplification of solution EE of some amino acids from 10-12 to 10-2, for period of several days.

Deposition of a newly identified Mesoproterozoic iron formation from the Dabie orogen: Influenced by high-T hydrothermal fluid and redox stratification

The mid-Proterozoic Eon (1.8–0.8 Ga; so-called “boring billion”) is a key interval in Earth’s history. Iron formations (IFs) have been used extensively as proxies for understanding the chemistry of the ancient seawater. However, there is limited information on IFs in this time window. Therefore, the dominant Fe source and depositional environment of IFs during this period remains enigmatic. Here, we report the first case of Mesoproterozoic IF, from Jiamiao in the Dabie orogen. Zircon U-Pb dating of two metavolcanics samples constrain the depositional age of the Jiamiao IF to be ca. 1359 Ma. The chemical composition of the IF samples, especially the strong positive Eu anomaly (Eu/Eu*PAAS = 3.94–6.96), suggest the role of high-T hydrothermal fluid in the IF deposition. The REY (rare earth element and yttrium) patterns and Ceanom (Ce anomaly) data in the studied IF and associated carbonates suggest a redoxcline separated the oxic surface ocean (at least > 1 % of the present atmospheric level) from ferruginous deeper water. In such a water column, the transport and dissolution of Mn-Fe (hydr)oxide particles across the redoxcline from oxidized surface water into deeper anoxic water, would lower the dissolved Y/Ho ratios, raise the LREE/HREE ratios, and increase the concentration of Ce relative to La and Pr. Integration of geochemical and isotopic data (C and O isotopes of marine origin) demonstrates that the composition of the Jiamiao IF and associated carbonates experienced mixing between seawater and a hydrothermal solution and Mn-Fe (hydr)oxide shuttling across a redoxcline.

Estimating the upper limit of Proterozoic petrographic organic carbon recycling

Atmospheric oxygen levels in the Proterozoic Eon are strongly debated, with estimates ranging from < 0.1 % – 10 % present atmospheric levels (PAL). A new approach to assess Proterozoic atmospheric oxygen levels based on the concentrations of recycled petrographic organic carbon in Proterozoic-aged strata indicates that atmospheric oxygen was potentially between 2 % and 24 % PAL. However, this model lacks some precision because the petrographic organic carbon flux in the Proterozoic is poorly constrained.This study focuses on marine siltstone and shale of the post-glacial Cryogenian Tapley Hill Formation (Adelaide Basin, south Australia) that was deposited during a eustatic transgression following the Sturtian glaciation. This strata contains concentrations of 0.041–0.754 wt% total organic carbon (TOC) and experienced burial diagenesis temperatures of 195 – 220 °C based on Raman spectroscopic characterization of disordered organic carbon. However, a portion of 12.4–58.1 % of the TOC within these rocks is of higher maturity, in part fully converted to graphite, and must therefore be recycled petrographic organic carbon of clastic origin. The measured proportion (%) of petrographic organic carbon increases with decreasing TOC concentration, resulting in petrographic organic carbon concentrations of 0.019 – 0.095 wt% (average 0.052 wt%).Because of potentially high post-glacial erosion rates, we presume that the reported petrographic organic carbon concentrations mark an upper limit on organic carbon recycling for the Proterozoic Eon. However, the diagenetic overprint of the Tapley Hill Formation in combination with petrographic similarities between graphitic and disordered organic carbon particles both indicate that the given values are a minimum estimate of petrographic organic carbon recycling and that the actual concentration of recycled organic carbon in the Tapley Hill Formation is higher. Therefore, we conclude that petrographic organic carbon recycling in the Neoproterozoic during the deposition of the Tapley Hill Formation was similar to modern marine depositional systems that display high organic carbon recycling rates. Because the weathering of petrographic organic carbon functions as a sink for atmospheric oxygen, high recycling rates during the Cryogenian period would allow for an increase in atmospheric oxygen concentrations.

Biogeochemical transformations after the emergence of oxygenic photosynthesis and conditions for the first rise of atmospheric oxygen.

The advent of oxygenic photosynthesis represents the most prominent biological innovation in the evolutionary history of the Earth. The exact timing of the evolution of oxygenic photoautotrophic bacteria remains elusive, yet these bacteria profoundly altered the redox state of the ocean-atmosphere-biosphere system, ultimately causing the first major rise in atmospheric oxygen (O2 )-the so-called Great Oxidation Event (GOE)-during the Paleoproterozoic (~2.5-2.2 Ga). However, it remains unclear how the coupled atmosphere-marine biosphere system behaved after the emergence of oxygenic photoautotrophs (OP), affected global biogeochemical cycles, and led to the GOE. Here, we employ a coupled atmospheric photochemistry and marine microbial ecosystem model to comprehensively explore the intimate links between the atmosphere and marine biosphere driven by the expansion of OP, and the biogeochemical conditions of the GOE. When the primary productivity of OP sufficiently increases in the ocean, OP suppresses the activity of the anaerobic microbial ecosystem by reducing the availability of electron donors (H2 and CO) in the biosphere and causes climate cooling by reducing the level of atmospheric methane (CH4 ). This can be attributed to the supply of OH radicals from biogenic O2 , which is a primary sink of biogenic CH4 and electron donors in the atmosphere. Our typical result also demonstrates that the GOE is triggered when the net primary production of OP exceeds >~5% of the present oceanic value. A globally frozen snowball Earth event could be triggered if the atmospheric CO2 level was sufficiently small (<~40 present atmospheric level; PAL) because the concentration of CH4 in the atmosphere would decrease faster than the climate mitigation by the carbonate-silicate geochemical cycle. These results support a prolonged anoxic atmosphere after the emergence of OP during the Archean and the occurrence of the GOE and snowball Earth event during the Paleoproterozoic.

Petrography and geochemistry of the iron-rich rocks in the banded iron formation of the Chilpi Group, Central India: Implications on the level of oxygen in the Paleoproterozoic atmosphere before the “Proterozoic iron ore gap”

The Chilpi Group (2050–1850 Ma) in the Bastar Craton contains Banded Iron Formation (BIF) deposited immediately after the Great Oxidation Event but before the “Proterozoic iron ore gap”. Baseline geochemical data generated from this crucial period of Earth's history representing the transition from an initial high productivity period followed by productivity collapse, thereby delaying the evolution of biota, are interpreted in terms of the redox state of the ocean and atmospheric oxygen content. Presence of chamosite, greenalite and siderite in the ironstones of the Chilpi Group, identified during present analysis, provide valuable information regarding the redox state of the shallow sea. Geochemical analyses reveal high concentrations of Fe2O3total and SiO2 (average ~ 87.85 wt%) in iron-rich bands. Trace elements commonly enriched in detrital phases (e.g. Sc, Hf, Nb, Th and Zr) show good correlation with total REE concentration, but these have concentration below the cut-off limit defined for detrital sediments (except 3 samples). Higher concentration of these elements in greenalite/chamosite-rich samples indicates accumulation of these elements in greenalite/chamosite during primary precipitation. Most of the samples have low concentrations of Al2O3 (<5 wt%) and TiO2 (<0.5 wt%), but some chamosite-bearing samples show enrichments of Al2O3 (up to ~20 wt%). Post-Archean Australian Shale normalised rare earth elements with Y (REEY) patterns, showing a superchondritic Y/Ho ratio (average 32.15) and positive La, Gd and Y anomalies, indicate the preservation of seawater like signatures. Though a low positive Eu-anomaly, and Al/(Al + Fe + Mn) versus Fe/Ti plot suggest seawater signature with possible mixing of hydrothermal fluids and/or <10 % detrital components, preservation of seawater signatures and no involvement of high-temperature hydrothermal fluids are deduced from Eu/Sm versus Sm/Yb and Eu/Sm versus Y/Ho patterns. The Eu/Sm and Y/Ho ratios lower than the seawater and a mixing trend away from oceanic hydrothermal solution indicate possible mixing of freshwater with seawater for the observed REEY patterns. Redox-sensitive trace element ratios indicate a dysoxic to suboxic-anoxic condition in the depositional basin. Presence of oolitic textures and occurrence of chamosite support the shallow water (<60 m water depth) and anoxic condition in the depositional basin. The oxygen content of 10−3–10−5 times the present atmospheric level in the atmosphere is inferred for the period during the deposition of the BIF.

Evidence of transient oxygenation in the Mesoproterozoic ocean from the Yanshan Basin, North China

Predominantly anoxic conditions with a heterogeneous stratified water column are widely accepted for the Mesoproterozoic ocean. However, transient and episodic oxygenation during the Mesoproterozoic has been recently hypothesized, which may have been an important trigger for eukaryote evolution. In this study, we analyzed the Ce anomalies of the Gaoyuzhuang and Hongshuizhuang formations in North China, to investigate the Earth’s surface environment during the Mesoproterozoic. Our data of negative Ce anomalies in the Gaoyuzhuang and Hongshuizhuang formations, reaching 0.73 and 0.84, respectively, suggest transient oxygenations of the surface environment. We applied a CeN/CeN* depth model to quantify these transient oxygenations and the results suggest that the atmospheric oxygen level would have increased by 0.01–0.03% present atmospheric level (PAL), 0.02–0.05% PAL, and 0.1–0.4% PAL, with the respective initial levels of 0.05% PAL, 0.1% PAL, and 1% PAL, in the Gaoyuzhuang and Hongshuizhuang formations. Our results suggest that although oxygen levels in the Mesoproterozoic were low, transient oxygenation may have occurred in the surface ocean, which would have provided vital niches for the evolution of eukaryotes.

The origin and distribution of the main oxygen sensing mechanism across metazoans.

Oxygen sensing mechanisms are essential for metazoans, their origin and evolution in the context of oxygen in Earth history are of interest. To trace the evolution of a main oxygen sensing mechanism among metazoans, the hypoxia induced factor, HIF, we investigated the phylogenetic distribution and phylogeny of 11 of its components across 566 eukaryote genomes. The HIF based oxygen sensing machinery in eukaryotes can be traced as far back as 800million years (Ma) ago, likely to the last metazoan common ancestor (LMCA), and arose at a time when the atmospheric oxygen content corresponded roughly to the Pasteur point, or roughly 1% of present atmospheric level (PAL). By the time of the Cambrian explosion (541-485Ma) as oxygen levels started to approach those of the modern atmosphere, the HIF system with its key components HIF1α, HIF1β, PHD1, PHD4, FIH and VHL was well established across metazoan lineages. HIF1α is more widely distributed and therefore may have evolved earlier than HIF2α and HIF3α, and HIF1β and is more widely distributed than HIF2β in invertebrates. PHD1, PHD4, FIH, and VHL appear in all 13 metazoan phyla. The O2 consuming enzymes of the pathway, PHDs and FIH, have a lower substrate affinity, Km, for O2 than terminal oxidases in the mitochondrial respiratory chain, in line with their function as an environmental signal to switch to anaerobic energy metabolic pathways. The ancient HIF system has been conserved and widespread during the period when metazoans evolved and diversified together with O2 during Earth history.

Extreme variability in atmospheric oxygen levels in the late Precambrian.

Mapping the history of atmospheric O2 during the late Precambrian is vital for evaluating potential links to animal evolution. Ancient O2 levels are often inferred from geochemical analyses of marine sediments, leading to the assumption that the Earth experienced a stepwise increase in atmospheric O2 during the Neoproterozoic. However, the nature of this hypothesized oxygenation event remains unknown, with suggestions of a more dynamic O2 history in the oceans and major uncertainty over any direct connection between the marine realm and atmospheric O2. Here, we present a continuous quantitative reconstruction of atmospheric O2 over the past 1.5 billion years using an isotope mass balance approach that combines bulk geochemistry and tectonic recycling rate calculations. We predict that atmospheric O2 levels during the Neoproterozoic oscillated between ~1 and ~50% of the present atmospheric level. We conclude that there was no simple unidirectional rise in atmospheric O2 during the Neoproterozoic, and the first animals evolved against a backdrop of extreme O2 variability.

Evaluating the Plausible Range of N2O Biosignatures on Exo-Earths: An Integrated Biogeochemical, Photochemical, and Spectral Modeling Approach

Nitrous oxide (N2O)—a product of microbial nitrogen metabolism—is a compelling exoplanet biosignature gas with distinctive spectral features in the near- and mid-infrared, and only minor abiotic sources on Earth. Previous investigations of N2O as a biosignature have examined scenarios using Earthlike N2O mixing ratios or surface fluxes, or those inferred from Earth’s geologic record. However, biological fluxes of N2O could be substantially higher, due to a lack of metal catalysts or if the last step of the denitrification metabolism that yields N2 from N2O had never evolved. Here, we use a global biogeochemical model coupled with photochemical and spectral models to systematically quantify the limits of plausible N2O abundances and spectral detectability for Earth analogs orbiting main-sequence (FGKM) stars. We examine N2O buildup over a range of oxygen conditions (1%–100% present atmospheric level) and N2O fluxes (0.01–100 teramole per year; Tmol = 1012 mole) that are compatible with Earth’s history. We find that N2O fluxes of 10 [100] Tmol yr−1 would lead to maximum N2O abundances of ∼5 [50] ppm for Earth–Sun analogs, 90 [1600] ppm for Earths around late K dwarfs, and 30 [300] ppm for an Earthlike TRAPPIST-1e. We simulate emission and transmission spectra for intermediate and maximum N2O concentrations that are relevant to current and future space-based telescopes. We calculate the detectability of N2O spectral features for high-flux scenarios for TRAPPIST-1e with JWST. We review potential false positives, including chemodenitrification and abiotic production via stellar activity, and identify key spectral and contextual discriminants to confirm or refute the biogenicity of the observed N2O.

Variability due to climate and chemistry in observations of oxygenated Earth-analogue exoplanets

ABSTRACT The Great Oxidation Event was a period during which Earth’s atmospheric oxygen (O2) concentrations increased from ∼10−5 times its present atmospheric level (PAL) to near modern levels, marking the start of the Proterozoic geological eon 2.4 billion years ago. Using WACCM6, an Earth System Model, we simulate the atmosphere of Earth-analogue exoplanets with O2 mixing ratios between 0.1 and 150 per cent PAL. Using these simulations, we calculate the reflection spectra over multiple orbits using the Planetary Spectrum Generator. We highlight how observer angle, albedo, chemistry, and clouds affect the simulated observations. We show that inter-annual climate variations, as well short-term variations due to clouds, can be observed in our simulated atmospheres with a telescope concept such as LUVOIR or HabEx. Annual variability and seasonal variability can change the planet’s reflected flux (including the reflected flux of key spectral features such as O2 and H2O) by up to factors of 5 and 20, respectively, for the same orbital phase. This variability is best observed with a high-throughput coronagraph. For example, HabEx (4 m) with a starshade performs up to a factor of two times better than a LUVOIR B (6 m) style telescope. The variability and signal-to-noise ratio of some spectral features depends non-linearly on atmospheric O2 concentration. This is caused by temperature and chemical column depth variations, as well as generally increased liquid and ice cloud content for atmospheres with O2 concentrations of &amp;lt;1 per cent PAL.

Is ozone a reliable proxy for molecular oxygen?

Molecular oxygen (O2) paired with a reducing gas is regarded as a promising biosignature pair for the atmospheric characterization of terrestrial exoplanets. In circumstances when O2 may not be detectable in a planetary atmosphere (e.g., at mid-IR wavelengths) it has been suggested that ozone (O3), the photochemical product of O2, could be used as a proxy to infer the presence of O2. However, O3 production has a nonlinear dependence on O2 and is strongly influenced by the UV spectrum of the host star. To evaluate the reliability of O3 as a proxy for O2, we used Atmos, a 1D coupled climate and photochemistry code, to study the O2–O3 relationship for “Earth-like” habitable zone planets around a variety of stellar hosts (G0V-M5V) and O2 abundances. Overall, we found that the O2–O3 relationship differed significantly with stellar hosts and resulted in different trends for hotter stars (G0V-K2V) versus cooler stars (K5V-M5V). Planets orbiting hotter host stars counter-intuitively experience an increase in O3 when O2 levels are initially decreased from 100% Earth’s present atmospheric level (PAL), with a maximum O3 abundance occurring at 25–55% PAL O2. As O2 abundance initially decreases, larger amounts of UV photons capable of O2 photolysis reach the lower (denser) regions of the atmosphere where O3 production is more efficient, thus resulting in these increased O3 levels. This effect does not occur for cooler host stars (K5V-M5V), since the weaker incident UV flux does not allow O3 formation to occur at dense enough regions of the atmosphere where the faster O3 production can outweigh a smaller source of O2 from which to create O3. Thus, planets experiencing higher amounts of incident UV possessed larger stratospheric temperature inversions, leading to shallower O3 features in planetary emission spectra. Overall it will be extremely difficult (or impossible) to infer precise O2 levels from an O3 measurement, however, with information about the UV spectrum of the host star and context clues, O3 will provide valuable information about potential surface habitability of an exoplanet.

High atmospheric CO2 levels in the early Mesoproterozoic estimated from paired carbon isotopic records from carbonates from North China

It is hypothesized that the Mesoproterozoic was characterized by a prevailing warm climate and a high atmospheric pCO2 level. However, quantitative constraints on Mesoproterozoic atmospheric pCO2 are scarce. Here, we report high-resolution organic and inorganic carbon isotope records from sediment samples aged ∼1.6 Ga, collected from Hebei Province in North China. The δ13Corg values of these Mesoproterozoic samples vary from −28.4‰ to −34.3‰, and the δ13Ccarbonate values range from −2.1‰ to 0.4‰. The paired carbonate and organic carbon isotope records can be used as a proxy to quantify the atmospheric CO2 concentration during the Mesoproterozoic. According to the calibration between the photosynthetic isotopic effect and atmospheric CO2, atmospheric CO2 concentrations are estimated to be within the range of 910–18,800 ppmv, ∼2–50 times greater than the present atmospheric level. The results support the previous hypothesis which suggests that high levels of atmospheric CO2 prevailed in the Early Mesoproterozoic. High atmospheric pCO2 levels could have played an important role in compensating for the possible lower solar luminosity and maintaining the temperature of the Mesoproterozoic Earth's surface.