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.

Sulfur-isotope anomalies recorded in Antarctic ice cores as a potential proxy for tracing past ozone layer depletion events.

Changes in the cosmic-ray background of the Earth can impact the ozone layer. High-energy cosmic events [e.g. supernova (SN)] or rapid changes in the Earth's magnetic field [e.g. geomagnetic Excursion (GE)] can lead to a cascade of cosmic rays. Ensuing chemical reactions can then cause thinning/destruction of the ozone layer-leading to enhanced penetration of harmful ultraviolet (UV) radiation toward the Earth's surface. However, observational evidence for such UV "windows" is still lacking. Here, we conduct a pilot study and investigate this notion during two well-known events: the multiple SN event (≈10 kBP) and the Laschamp GE event (≈41 kBP). We hypothesize that ice-core-Δ33S records-originally used as volcanic fingerprints-can reveal UV-induced background-tropospheric-photochemical imprints during such events. Indeed, we find nonvolcanic S-isotopic anomalies (Δ33S ≠ 0‰) in background Antarctic ice-core sulfate during GE/SN periods, thereby confirming our hypothesis. This suggests that ice-core-Δ33S records can serve as a proxy for past ozone-layer-depletion events.