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 δ¹³C₀rg 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

Anaerobic nitrogen cycling on a Neoarchaean ocean margin

A persistently aerobic marine nitrogen cycle featuring the biologically mediated oxidation of ammonium to nitrate has likely been in place since the Great Oxidation Event (GOE) some 2.3 billion years ago. Although nitrogen isotope data from some Neoarchaean sediments suggests transient nitrate availability prior to the GOE, these data are open to other interpretations. This is especially so as these data come from relatively deep-water environments that were spatially divorced from shallow-water settings that were the most likely sites for the accumulation of oxygen and the generation of nitrate. Here we present the first nitrogen isotope data from contemporaneous shallow-water sediments to constrain the nitrogen cycle in shallow Late Archaean settings. The BH-1 Sacha core through the Campbellrand-Malmani carbonate platform records a transition from a shallow siliciclastic/carbonate ramp to a rimmed carbonate shelf with the potential for reduced communication with the open ocean. In these settings nitrogen isotope (δ15N) data from sub- to peri-tidal and lagoonal settings are close to 0‰, indicating diazotrophy or the complete utilization of remineralised ammonium with an isotopic composition of near 0‰. Our dataset also includes negative δ15N values that suggest the presence of an ammonium pool of concentrations sufficient to have allowed for non-quantitative assimilation. We suggest that this condition may have been the result of upwelling of phosphorus-rich deep waters into the photic zone, stimulating primary productivity and creating an enhanced flux of organic matter that was subsequently remineralised and persisted in the dominantly anoxic Neoarchaean marine environment. Notably, we find only limited evidence of coupled nitrification/denitrification, even in these shallow water environments, calling into question previous suggestions that the Late Archaean nitrogen cycle was characterized by widespread aerobic nitrogen cycling. Rather, aerobic nitrogen cycling was likely spatially heterogeneous and tied to loci of high oxygen production while zones of shallow water anoxia persisted

The ineluctable requirement for the trans-iron elements molybdenum and/or tungsten in the origin of life

An evolutionary tree of key enzymes from the Complex-Iron-Sulfur-Molybdoenzyme (CISM) superfamily distinguishes “ancient” members, i.e. enzymes present already in the last universal common ancestor (LUCA) of prokaryotes, from more recently evolved subfamilies. The majority of the presented subfamilies and, as a consequence, the Molybdo-enzyme superfamily as a whole, appear to have existed in LUCA. The results are discussed with respect to the nature of bioenergetic substrates available to early life and to problems arising from the low solubility of molybdenum under conditions of the primordial Earth

Marine oxygen production and open water supported an active nitrogen cycle during the Marinoan Snowball Earth

The Neoproterozoic Earth was punctuated by two low-latitude Snowball Earth glaciations. Models permit oceans with either total ice cover or substantial areas of open water. Total ice cover would make an anoxic ocean likely, and would be a formidable barrier to biologic survival. However, there are no direct data constraining either the redox state of the ocean or marine biological productivity during the glacials. Here we present iron-speciation, redox-sensitive trace element, and nitrogen isotope data from a Neoproterozoic (Marinoan) glacial episode. Iron-speciation indicates deeper waters were anoxic and Fe-rich, while trace element concentrations indicate surface waters were in contact with an oxygenated atmosphere. Furthermore, synglacial sedimentary nitrogen is isotopically heavier than the modern atmosphere, requiring a biologic cycle with nitrogen fixation, nitrification and denitrification. Our results indicate significant regions of open marine water and active biologic productivity throughout one of the harshest glaciations in Earth history

Earth: Atmospheric Evolution of a Habitable Planet

Our present-day atmosphere is often used as an analog for potentially habitable exoplanets, but Earth's atmosphere has changed dramatically throughout its 4.5 billion year history. For example, molecular oxygen is abundant in the atmosphere today but was absent on the early Earth. Meanwhile, the physical and chemical evolution of Earth's atmosphere has also resulted in major swings in surface temperature, at times resulting in extreme glaciation or warm greenhouse climates. Despite this dynamic and occasionally dramatic history, the Earth has been persistently habitable--and, in fact, inhabited--for roughly 4 billion years. Understanding Earth's momentous changes and its enduring habitability is essential as a guide to the diversity of habitable planetary environments that may exist beyond our solar system and for ultimately recognizing spectroscopic fingerprints of life elsewhere in the Universe. Here, we review long-term trends in the composition of Earth's atmosphere as it relates to both planetary habitability and inhabitation. We focus on gases that may serve as habitability markers (CO2, N2) or biosignatures (CH4, O2), especially as related to the redox evolution of the atmosphere and the coupled evolution of Earth's climate system. We emphasize that in the search for Earth-like planets we must be mindful that the example provided by the modern atmosphere merely represents a single snapshot of Earth's long-term evolution. In exploring the many former states of our own planet, we emphasize Earth's atmospheric evolution during the Archean, Proterozoic, and Phanerozoic eons, but we conclude with a brief discussion of potential atmospheric trajectories into the distant future, many millions to billions of years from now. All of these 'Alternative Earth' scenarios provide insight to the potential diversity of Earth-like, habitable, and inhabited worlds.Comment: 34 pages, 4 figures, 4 tables. Review chapter to appear in Handbook of Exoplanet