RESUMEN
Cyanide and its derivatives play important roles in prebiotic chemistry through a variety of possible mechanisms. In particular, cyanide has been shown to allow for the synthesis of ribonucleotides and amino acids. Although dissolved hydrogen cyanide can be lost as a gas or undergo hydrolysis reactions, cyanide can also potentially be stored and stockpiled as ferrocyanide (Fe(CN)6-4), which is more stable. Furthermore, ferrocyanide aids in some prebiotic synthetic reactions. Here, we investigate the formation rates and yields of ferrocyanide as a function of various environmental parameters, such as the pH, temperature, and concentration. We find that ferrocyanide formation rates and yields are optimal at slightly alkaline conditions (pH 8-9) and moderate temperatures (≈20-30 °C). Given the wide range of possible lake environments likely available on early Earth, our results help to constrain the environmental conditions that would favor cyanide- and ferrocyanide-based prebiotic chemistries. We construct lake box models and find that ferrocyanide may be able to form and reach significant concentrations for prebiotic chemistry on the time scale of years under favorable conditions.
RESUMEN
The Great Oxidation Event (GOE), arguably the most important event to occur on Earth since the origin of life, marks the time when an oxygen-rich atmosphere first appeared. However, it is not known whether the change was abrupt and permanent or fitful and drawn out over tens or hundreds of millions of years. Here, we developed a one-dimensional time-dependent photochemical model to resolve time-dependent behavior of the chemically unstable transitional atmosphere as it responded to changes in biogenic forcing. When forced with step-wise changes in biogenic fluxes, transitions between anoxic and oxic atmospheres take between only 102 and 105 y. Results also suggest that O2 between [Formula: see text] and [Formula: see text] mixing ratio is unstable to plausible atmospheric perturbations. For example, when atmospheres with these O2 concentrations experience fractional variations in the surface CH4 flux comparable to those caused by modern Milankovich cycling, oxygen fluctuates between anoxic ([Formula: see text]) and oxic ([Formula: see text]) mixing ratios. Overall, our simulations are consistent with possible geologic evidence of unstable atmospheric O2, after initial oxygenation, which could occasionally collapse from changes in biospheric or volcanic fluxes. Additionally, modeling favors mid-Proterozoic O2 exceeding [Formula: see text] to [Formula: see text] mixing ratio; otherwise, O2 would periodically fall below [Formula: see text] mixing ratio, which would be inconsistent with post-GOE absence of sulfur isotope mass-independent fractionation.