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Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the Earth's early atmosphere

Zahnle, Kevin J.·1986·Journal of Geophysical Research: Atmospheres

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Abstract

The photochemistries of methane and HCN are discussed in the context of the primitive terrestrial atmosphere, using a detailed numerical model. In the absence of abundant O 2, absorption of solar EUV (λ < 1023Å) by N 2 provides a large thermospheric source of atomic nitrogen. Methane is oxidized cleanly and efficiently, provided CO 2 is more abundant than CH 4. Otherwise, a large fraction of the methane present is polymerized, forming alkanes in the troposphere and polyacetylenes and nitriles in the upper atmosphere. The combination of low O 2, high N 2, and moderately high levels of CO 2 would have made the ancient terrestrial atmosphere a favorable environment for the production of HCN from CH 4. 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 hydrocyanic acid rain. For larger methane sources exceeding a critical value of order 10 11 molecules cm−2 s−1 (corresponding to ƒ(CH 4) 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 NH 3 mixing ratios approaching 1 ppm.

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Authors: Zahnle, K. J.
Corresponding author: Zahnle, Kevin J.
ORCID: Zahnle, Kevin J.
Venue: Journal of Geophysical Research: Atmospheres
Publisher: American Geophysical Union (AGU)
Published: 1986-02-20
Volume: 91
Issue: D2
Pages: 2819-2834
ISSN: 0148-0227 (ISSN-L)
DOI: 10.1029/jd091id02p02819
OpenAlex: W1965198394
Cited by: 276
References: 123
Citations by year: 2026: 10 · 2025: 18 · 2024: 13 · 2023: 7 · 2022: 18 · 2021: 10 · 2020: 16 · 2019: 20 · 2018: 17 · 2017: 7 · 2016: 11 · 2015: 11 · 2014: 6 · 2013: 8 · 2012: 4
FWCI: 4.19
Type: journal article
Language: en
Open access: closed
Licence: onlinelibrary.wiley.com/termsAndConditions#vor (vor, 9710 d)
Locations: Journal of Geophysical Research Atmospheres (publishedVersion)
Topics: Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Atmospheric chemistry and aerosols
Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
Physical Sciences › Earth and Planetary Sciences › Space and Planetary Science › Astro and Planetary Science
Keywords: methane photochemistry, hydrogen cyanide, early Earth atmosphere, atomic nitrogen, methane oxidation, polyacetylene, nitriles, atmospheric transport, turbulent diffusion, ammonia, carbon cycle, CO2 abundance

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Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the Earth's early atmosphere

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