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Context. Lightning has been suggested to play a role in triggering the occurrence of bio-ready chemical species. Future missions such as PLATO, ARIEL, HWO, and LIFE, as well as ground-based extremely large telescopes (ELTs), will carry out investigations of the atmospheres of potentially habitable exoplanets. Aims. We aim to study the effect of lightning on the atmospheric chemistry. We also consider how it affects false-positive and false-negative biosignatures and whether these effects would be observable on exo-Earth and TRAPPIST-1 planets. Methods. We utilised a combination of laboratory experiments and photochemical and radiative transfer modelling. We conducted spark discharge experiments in N2−CO2−H2 gas mixtures, representing a range of possible rocky-planet atmospheres. We investigated the production of potential lightning signatures (CO and NO), possible biosignature gases (N2O, NH3, and CH4), and important prebiotic precursors (HCN and urea). Using the measured CO and NO production rates, we conducted photochemical simulations for oxygen-rich and anoxic atmospheres for rocky planets orbiting in the habitable zones of the Sun and TRAPPIST-1 for a range of lightning flash rates. Synthetic spectra were calculated using SMART to study the atmosphere’s reflectance, along with the emission and transmission spectra. Results. Lightning enhances the spectral features of NO, NO2, and (in some cases) CO through direct production; whereas CH4 and C2H6 may be enhanced indirectly. Lightning at a flash rate slightly higher than on modern-day Earth is able to mask the ozone features of an oxygen-rich, biotic atmosphere, making it harder to detect the biosphere of such a planet. Similarly, lightning at a flash rate at least ten times higher than on modern-day Earth is also able to mask the presence of ozone in the anoxic, abiotic atmosphere of a planet orbiting a late M dwarf, reducing the potential for a false-positive life detection. Conclusions. The threshold lightning flash rates to eliminate oxygen (>0.1%) and ozone false positive biosignatures on planets orbiting ultra-cool dwarfs is up to ten times higher than the modern flash rate. This result indicates that lightning cannot always prevent these false-positive scenarios.

The Archean Eon was a time of predominantly anoxic Earth surface conditions, where anaerobic processes controlled bioessential element cycles. In contrast to "oxygen oases" well documented for the Neoarchean [2.8 to 2.5 billion years ago (Ga)], the magnitude, spatial extent, and underlying causes of possible Mesoarchean (3.2 to 2.8 Ga) surface-ocean oxygenation remain controversial. Here, we report δ15N and δ13C values coupled with local seawater redox data for Mesoarchean shales of the Mozaan Group (Pongola Supergroup, South Africa) that were deposited during an episode of enhanced Mn (oxyhydr)oxide precipitation between ∼2.95 and 2.85 Ga. Iron and Mn redox systematics are consistent with an oxygen oasis in the Mesoarchean anoxic ocean, but δ15N data indicate a Mo-based diazotrophic biosphere with no compelling evidence for a significant aerobic nitrogen cycle. We propose that in contrast to the Neoarchean, dissolved O2 levels were either too low or too limited in extent to develop a large and stable nitrate reservoir in the Mesoarchean ocean. Since biological N2 fixation was evidently active in this environment, the growth and proliferation of O2-producing organisms were likely suppressed by nutrients other than nitrogen (e.g., phosphorus), which would have limited the expansion of oxygenated conditions during the Mesoarchean.

Boron geochemistry from biogenic carbonates offer valuable information about ocean pH and CO2 chemistry. However, application to geological carbonate deposits suffers from analytical difficulties in obtaining geochemical signals exclusively from the carbonate phase. Sequential leaching with reagents and acids has the potential to overcome such an issue. There is, however, little systematic investigation about the efficiency of sequential leaching in isolating carbonate‐associated boron from siliciclastic matrix. Here, we developed a sequential leaching protocol and applied it to methane‐derived‐authigenic‐carbonate samples. Using the leachate δ11B signatures, elemental composition, and mineral composition of residues, we show that the sequential leaching is able to improve the separation of boron from different phases. Buffered hydrogen peroxide removes organic matter and also some silicate phases resulting low δ11B values. Leaching with NH4Ac removes adsorbed boron though may also partially leach some carbonate phases. The first few leaching steps with diluted acetic acid dissolve carbonate phases. Depending on the sample type, these may also capture some remaining adsorbed boron from the preceding NH4Ac leaching. Once the adsorbed boron is completely removed, as indicated by the progressively higher δ11B values during the following acid leaching steps, representative carbonate composition can be derived. The accuracy of this protocol is demonstrated with leaching experiments using artificial deep sea coral carbonate and clay mixtures that give the representative carbonate‐associated δ11B within error of the pure coral value. Our results provide insights into characteristic signatures derived from silicates and organic matter that need to be considered in boron isotope analyses of impure marine carbonates. Key Points: Boron signals from geological carbonate deposits are difficult to isolate from siliciclastic components of mixed matrix samplesA calibrated sequential leaching protocol was developed to extract boron from the carbonate phase of mixed carbonate‐silicate limestonesSuccessful separation is possible in samples with only 25% carbonate, provided the protocol is adjusted for carbonate content [ABSTRACT FROM AUTHOR]

It has been proposed that an "oxygen overshoot" occurred during the early Paleoproterozoic Great Oxidation Event (GOE) in association with the extreme positive carbon isotopic excursion known as the Lomagundi Event. Moreover, it has also been suggested that environmental oxygen levels then crashed to very low levels during the subsequent extremely negative Shunga-Francevillian carbon isotopic anomaly. These redox fluctuations could have profoundly influenced the course of eukaryotic evolution, as eukaryotes have several metabolic processes that are obligately aerobic. Here we investigate the magnitude of these proposed oxygen perturbations using selenium (Se) geochemistry, which is sensitive to redox transitions across suboxic conditions. We find that δ82/78Se values in offshore shales show a positive excursion from 2.32 Ga until 2.1 Ga (mean +1.03 ± 0.67‰). Selenium abundances and Se/TOC (total organic carbon) ratios similarly show a peak during this interval. Together these data suggest that during the GOE there was pervasive suboxia in near-shore environments, allowing nonquantitative Se reduction to drive the residual Se oxyanions isotopically heavy. This implies O2 levels of >0.4 μM in these settings. Unlike in the late Neoproterozoic and Phanerozoic, when negative δ82/78Se values are observed in offshore environments, only a single formation, evidently the shallowest, shows evidence of negative δ82/78Se. This suggests that there was no upwelling of Se oxyanions from an oxic deep-ocean reservoir, which is consistent with previous estimates that the deep ocean remained anoxic throughout the GOE. The abrupt decline in δ82/78Se and Se/TOC values during the subsequent Shunga-Francevillian anomaly indicates a widespread decrease in surface oxygenation.

Deep‐marine brine seeps in the modern ocean are considered analogs for settings that favored the formation of sedimentary‐exhalative zinc and lead deposits in deep time. Microbial activity plays an important role in the accumulation of ore minerals, meaning that the extent of mineralization is at least indirectly dependent on nutrient fluxes. Here, we investigated the biogeochemical nitrogen cycle in shallow (15–50 cm) sediment cores from the Orca Basin brine pool and surrounding sites, as well as from an active brine seep area near Dead Crab Lake in the Gulf of Mexico, with the aim of constraining the effect of brine seepage on this bio‐essential element. We find high porewater ammonium concentrations in the millimolar range, paired with elevated ratios of organic carbon to nitrogen in sediments, which confirm previous hypotheses that the brine recycles ammonium from sedimentary strata back into the water column. Within Orca Basin, we note tentative evidence of microbial ammonium utilization. At the active seep, ammonium is mixed into the overlying water column and likely undergoes oxidation. Isotopic data from sediments and dissolved ammonium, paired with previously published genomic data, suggest the presence of dissimilatory nitrate reduction to ammonium at the brine‐seawater interface. We conclude that brine seeps can stimulate biological nitrogen metabolisms in multiple ways. Our results may help calibrate studies of biogeochemical cycles around brine seeps that are archived in the rock record. Plain Language Summary: Brine seeps in the deep ocean are sites where fluids with exceptionally high salinity, up to 10 times that of seawater, seep up through marine sediments and are dispersed into the water column. Such saline fluids can carry high concentrations of metals such as iron, zinc, lead and copper, and therefore brine seeps have been proposed as mechanisms for the formation of ore deposits in the past. An important aspect in this theory is that high microbial activity of primary and secondary producers near the brine seeps creates locally anoxic conditions under which metals are trapped in sulfide minerals. Such biological activity would require input of nutrients, including nitrogen. To shed more light on the biogeochemical nitrogen cycle in brine seeps, we investigated nitrogen isotopes and abundances in samples from the Gulf of Mexico. Here, ammonium concentrations in the millimolar range have previously been documented. Our results support the idea that nitrogen is leached by the brines from deeper sediments and released into the overlying water column. Furthermore, we find evidence for specific microbial metabolisms that are stimulated by mixing between anoxic brine fluids and oxygenated seawater, which may also have occurred in past ore‐forming environments. Key Points: Brine seeps in the Gulf of Mexico recycle bioavailable nitrogen from sediments back into the water columnNitrogen isotopes suggest that brine seepage stimulates biological activity, including dissimilatory nitrate reduction to ammoniumBiological productivity stimulated by brine seeps may have contributed to the formation of sedimentary ore deposits [ABSTRACT FROM AUTHOR]