Mechanistic Links Between the Sedimentary Redox Cycle and Marine Acid-Base Chemistry

The redox state of Earth's surface is controlled on geological timescales by the flow of electrons through the sedimentary rock cycle, mediated largely by the weathering and burial of C‐S‐Fe phases. These processes buffer atmospheric pO₂. At the same time, CO₂ influxes and carbonate burial control seawater acid‐base chemistry and climate over long timescales via the carbonate‐silicate cycle. However, these two systems are mechanistically linked and impact each other via charge balance in the hydrosphere. Here, we use a low‐order Earth system model to interrogate a subset of these connections, with a focus on changes that occur during perturbations to electron flow through the sedimentary rock cycle. We show that the net oxidation or reduction of the Earth's surface can play an important role in controlling acid‐base processes in the oceans and thus climate, and suggest that these links should be more fully integrated into interpretive frameworks aimed at understanding Earth system evolution throughout Precambrian and Phanerozoic time

Mechanistic Links Between the Sedimentary Redox Cycle and Marine Acid-Base Chemistry

The redox state of Earth's surface is controlled on geological timescales by the flow of electrons through the sedimentary rock cycle, mediated largely by the weathering and burial of C‐S‐Fe phases. These processes buffer atmospheric pO₂. At the same time, CO₂ influxes and carbonate burial control seawater acid‐base chemistry and climate over long timescales via the carbonate‐silicate cycle. However, these two systems are mechanistically linked and impact each other via charge balance in the hydrosphere. Here, we use a low‐order Earth system model to interrogate a subset of these connections, with a focus on changes that occur during perturbations to electron flow through the sedimentary rock cycle. We show that the net oxidation or reduction of the Earth's surface can play an important role in controlling acid‐base processes in the oceans and thus climate, and suggest that these links should be more fully integrated into interpretive frameworks aimed at understanding Earth system evolution throughout Precambrian and Phanerozoic time

A Limited Habitable Zone for Complex Life

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.Comment: Revised including additional discussion. Published Gold OA in ApJ. 9 pages, 5 figures, 5 table

Long-term sedimentary recycling of rare sulphur isotope anomalies

The accumulation of substantial quantities of O_2 in the atmosphere has come to control the chemistry and ecological structure of Earth’s surface. Non-mass-dependent (NMD) sulphur isotope anomalies in the rock record are the central tool used to reconstruct the redox history of the early atmosphere. The generation and initial delivery of these anomalies to marine sediments requires low partial pressures of atmospheric O_2 (PO_2; refs 2, 3), and the disappearance of NMD anomalies from the rock record 2.32 billion years ago is thought to have signalled a departure from persistently low atmospheric oxygen levels (less than about 10^(−5) times the present atmospheric level) during approximately the first two billion years of Earth’s history. Here we present a model study designed to describe the long-term surface recycling of crustal NMD anomalies, and show that the record of this geochemical signal is likely to display a ‘crustal memory effect’ following increases in atmospheric PO_2 above this threshold. Once NMD anomalies have been buried in the upper crust they are extremely resistant to removal, and can be erased only through successive cycles of weathering, dilution and burial on an oxygenated Earth surface. This recycling results in the residual incorporation of NMD anomalies into the sedimentary record long after synchronous atmospheric generation of the isotopic signal has ceased, with dynamic and measurable signals probably surviving for as long as 10–100 million years subsequent to an increase in atmospheric PO_2 to more than 10^(−5) times the present atmospheric level. Our results can reconcile geochemical evidence for oxygen production and transient accumulation with the maintenance of NMD anomalies on the early Earth, and suggest that future work should investigate the notion that temporally continuous generation of new NMD sulphur isotope anomalies in the atmosphere was likely to have ceased long before their ultimate disappearance from the rock record

A comprehensive sulfur and oxygen isotope study of sulfur cycling in a shallow, hyper-euxinic meromictic lake

Mahoney Lake is a permanently anoxic and sulfidic (euxinic) lake that has a dense plate of purple sulfur bacteria positioned at mid-water depth (∼7 m) where free sulfide intercepts the photic zone. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and the water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within an aquatic environment with extremely high sulfide concentrations (>30 mM). Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S > 50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake, sulfur disproportionation is likely inoperable or limited to a very narrow zone in the chemocline, and therefore the large instantaneous fractionations are best explained by the microbial process of sulfate reduction. Pyrite extracted from the sediments reflects the isotopic composition of water column sulfide, suggesting that pyrite buried in the euxinic depocenter of the lake formed in the water column. The offset between sulfate and dissolved sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by elevated sulfate reduction rates and inconsistent with appreciable disproportionation within this interval. Water column sulfate exhibits a linear response in δ18OSO4–δ34SSO4 and the slope of this relationship suggests relatively high sulfate reduction rates that appear to respond to seasonal changes in the productivity of purple sulfur bacteria. Although photosynthetic activity within the microbial plate influences the δ18OSO4–δ34SSO4 relationship, the biosignature for photosynthetic sulfur bacteria is restricted to the oxic/anoxic transition zone and is apparently minor relative to the more prevalent process of sulfate reduction operative throughout the light-deprived deeper anoxic water column and sediment pore waters