Photochemistry of Methane and the Formation of Hydrocyanic Acid (HCN) in the Earth’s Early Atmosphere

The photochemistries of methane and HCN are discussed in the context of the primitive terrestrial atmosphere,using a detailed numerical model. In the absenceof abundant O2, absorption of solar EUV (λ < 1023Å) by N2 provides a large thermosphersic source of atomic nitrogen. Methane is oxidized cleanly and efficiently,provided CO2 is more abundant than CH,•. Otherwise,a large fraction of the methane present is polymerized, forming alkanes in the troposphere and polyacetylenes and nitriles in the upper atmosphere. The combinationof low 02, high N2, and moderately high levels of CO2 would have made the ancient terrestrial atmosphere a favorable environment for the production of HCN from CH4. Once formed, HCN is rather long-lived; it is removed from the atmosphere either by direct photodissociation at Ly α (~100 years) or by rainfall (~10 years). Chemical loss would have been unimportant. Owing to its stability, transport of HCN from the top to the bottom of the atmosphere can be efficient; nevertheless, our results are sensitive to the assumed eddy diffusion profile. For small amounts of methane a small constant fraction of order 0.1% to 1% of the carbon in the methane is returned to the surface as hydrocyanicacid rain. For larger methane sources exceeding a critical value of order 10^11 molecules c cm^(-2) s^(-1) (corresponding to f(CH4) of order 10-4-10-3), rainout of HCN increases abruptly to more than 10% of the carbon supplied as methane,limited by the primary production of N. Under favorable conditions, hydrolysis of HCN could have supported atmospheric NH3 mixing ratios approaching 1 ppm.

Authors: K. Zahnle

https://doi.org/10.1029/JD091iD02p02819