Fixed nitrogen species generated by the early Earth's atmosphere are thought to be critical to the emergence of life and the sustenance of early metabolisms. A previous study estimated nitrogen fixation in the Hadean Earth's N2/CO2-dominated atmosphere; however, that previous study only considered a limited chemical network that produces NOx species (i.e., no HCN formation) via the thermochemical dissociation of N2 and CO2 in lightning flashes, followed by photochemistry. Here, we present an updated model of nitrogen fixation on Hadean Earth. We use the Chemical Equilibrium with Applications (CEA) thermochemical model to estimate lightning-induced NO and HCN formation and an updated version of KINETICS, the 1-D Caltech/JPL photochemical model, to assess the photochemical production of fixed nitrogen species that rain out into the Earth's early ocean. Our updated photochemical model contains hydrocarbon and nitrile chemistry, and we use a Geant4 simulation platform to consider nitrogen fixation stimulated by solar energetic particle deposition throughout the atmosphere. We study the impact of a novel reaction pathway for generating HCN via HCN2, inspired by the experimental results which suggest that reactions with CH radicals (from CH4 photolysis) may facilitate the incorporation of N into the molecular structure of aerosols. When the HCN2 reactions are added, we find that the HCN rainout rate rises by a factor of five in our 1-bar case and is about the same in our 2- and 12-bar cases. Finally, we estimate the equilibrium concentration of fixed nitrogen species under a kinetic steady state in the Hadean ocean, considering loss by hydrothermal vent circulation, photoreduction, and hydrolysis. These results inform our understanding of environments that may have been relevant to the formation of life on Earth, as well as processes that could lead to the emergence of life elsewhere in the universe.

Solar-induced chlorophyll fluorescence (SIF) is widely accepted as a proxy for gross primary productivity (GPP). Among the various SIF measurements, tower-based SIF measurements allow for continuous monitoring of SIF variation at a canopy scale with high temporal resolution, making it suitable for monitoring highly variable plant physiological responses to environmental changes. However, because of the strong and close relationship between SIF and absorbed photosynthetically active radiation (aPAR), it may be difficult to detect the influence of environmental drivers other than light conditions. Among the drivers, atmospheric dryness (vapor pressure deficit, VPD) is projected to increase as drought becomes more frequent and severe in the future, negatively impacting plants. In this study, we evaluated the tower-based high-frequency SIF measurement as a tool for detecting plant response to highly variable VPD. The study was performed in a mixed temperate forest in Virginia, USA, where a 40-m-tall flux tower has been measuring gas and energy exchanges and ancillary environmental drivers, and the Fluospec 2 system has been measuring SIF. We show that a proper definition of light availability to vegetation can reproduce SIF response to changing VPD that is comparable to GPP response as estimated from eddy covariance measurement: GPP decreased with rising VPD regardless of how aPAR was defined, whereas SIF decreased only when aPAR was defined as the PAR absorbed by chlorophyll (aPAR(chl)) or simulated by a model (Soil Canopy Observation, Photochemistry and Energy fluxes, SCOPE). We simulated the effect of VPD on SIF with two different simulation modes of fluorescence emission representing contrasting moisture conditions, 'Moderate' and 'Soil Moisture (SM) Stress' modes. The decreasing SIF to rising VPD was only found in the SM Stress mode, implying that the SIF-VPD relationship depends on soil moisture conditions. Furthermore, we observed a similar response of SIF to VPD at hourly and daily scales, indicating that satellite measurements can be used to study the effects of environmental drivers other than light conditions. Finally, the definition of aPAR emphasizes the importance of canopy structure research to interpret remote sensing observations properly.