Biogenic Methane, Hydrogen Escape, and the Irreversible Oxidation of Early Earth

Catling, David C.; Zahnle, Kevin J.; McKay, Christopher P.

doi:10.1126/science.1061976

Cited by 507Paleontology and Stratigraphy of FossilsOrigins and Evolution of LifeEarth Systems and Cosmic Evolution

Biogenic Methane, Hydrogen Escape, and the Irreversible Oxidation of Early Earth

Catling, David C., Zahnle, Kevin J., McKay, Christopher P.·2001·Science

DOI 10.1126/science.1061976

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Abstract

The low O 2 content of the Archean atmosphere implies that methane should have been present at levels ∼10 2 to 10 3 parts per million volume (ppmv) (compared with 1.7 ppmv today) given a plausible biogenic source. CH 4 is favored as the greenhouse gas that countered the lower luminosity of the early Sun. But abundant CH 4 implies that hydrogen escapes to space (↑space) orders of magnitude faster than today. Such reductant loss oxidizes the Earth. Photosynthesis splits water into O 2 and H, and methanogenesis transfers the H into CH 4 . Hydrogen escape after CH 4 photolysis, therefore, causes a net gain of oxygen [CO 2 + 2H 2 O → CH 4 + 2O 2 → CO 2 + O 2 + 4H(↑space)]. Expected irreversible oxidation (∼10 12 to 10 13 moles oxygen per year) may help explain how Earth's surface environment became irreversibly oxidized.

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This hydrogen was likely derived from UV photolysis of CH4 in the upper atmosphere.
“This hydrogen was likely derived from UV photolysis of CH4 in the upper atmosphere (135).”
From The Archean atmosphere (2020) · cites this paper as [135]
Some emphasize the role of hydrogen escape to space in oxidizing solid Earth, lowering Earth's capacity to release O2-consuming reductants.
“Some emphasize the role of hydrogen escape to space in oxidizing solid Earth, lowering Earth’s capacity to release O2-consuming reductants (121, 135, 136).”
From The Archean atmosphere (2020) · cites this paper as [135]
Anoxic Archean air could hold 1000s of ppmv of CH4 if a microbial flux of CH4 was comparable to today's.
“Anoxic Archean air could hold 1000 s of parts per million by volume of CH4 if a microbial flux of CH4 was comparable to today’s (135, 183, 184).”
From The Archean atmosphere (2020) · cites this paper as [135]
Assuming crust oxidation (resulting in a present Fe3+ excess of ≈2 × 1021 mol O2 eq) is linked to continental growth, an 'episodic continental growth' model with rapid growth from 10 to 80% of present area 3.2-2.5 Ga would imply a net oxidation rate of ≈2 × 1012 mol O2 eq yr−1.
“For example, assuming crust oxidation (resulting in a present Fe3+ excess54 of ≈2 × 1021 mol O2 eq) is linked to continental growth, an ‘episodic continental growth' model55 with rapid growth from 10 to 80% of present area 3.2–2.5 Ga would imply a net oxidation rate of ≈2 × 1012 mol O2 eq yr−1 (balanced by a combination of hydrogen escape and organic carbon accumulation).”
From Atmospheric oxygen regulation at low Proterozoic levels by incomplete oxidative weathering of sedimentary organic carbon (2017) · cites this paper as [54]
There are 3.7 × 1019 mol O2 in the atmosphere and oceans, 5.1 × 1020 mol O2 equivalent Fe3+ and sulfate in sedimentary rocks, and ~2 × 1021 mol O2 equivalent excess Fe3+ in igneous and metamorphic rocks.
“Although there are 3.7 × 1019 mol O2 in the atmosphere and oceans, there are 5.1 × 1020 mol O2 equivalent Fe3+ and sulfate in sedimentary rocks, and ~2 × 1021 mol O2 equivalent excess Fe3+ in igneous and metamorphic rocks (68).”
From Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life (2018) · cites this paper as [68]

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Authors: Catling, D. C., Zahnle, K. J., & McKay, C. P.
Affiliations: Ames Research Center (US)
Corresponding author: Catling, David C.
ORCID: Catling, David C.
Zahnle, Kevin J.
McKay, Christopher P.
Venue: Science
Publisher: American Association for the Advancement of Science (AAAS)
Published: 2001-08-03
Volume: 293
Issue: 5531
Pages: 839-843
ISSN: 0036-8075 (ISSN-L)
1095-9203
DOI: 10.1126/science.1061976
OpenAlex: W1972615373
Cited by: 507
References: 39
Citations by year: 2026: 18 · 2025: 20 · 2024: 24 · 2023: 13 · 2022: 25 · 2021: 28 · 2020: 33 · 2019: 21 · 2018: 26 · 2017: 18 · 2016: 14 · 2015: 15 · 2014: 10 · 2013: 26 · 2012: 18
FWCI: 17.72
Type: journal article
Language: en
Open access: closed
Locations: Science (publishedVersion)
PubMed (publishedVersion)
Bristol Research (University of Bristol) (publishedVersion)
Explore Bristol Research (submittedVersion)
Topics: Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Earth Systems and Cosmic Evolution
Keywords: biogenic methane, hydrogen escape, Archean atmosphere, methanogenesis, greenhouse effect, photosynthesis
MeSH terms: Atmosphere, Bacteria, Carbon Dioxide, Climate, Hydrogen, Iron, Methane, Oxidation-Reduction, Oxygen, Photosynthesis, Sulfur, Earth, Planet, Geologic Sediments, Evolution, Planetary, Euryarchaeota

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Biogenic Methane, Hydrogen Escape, and the Irreversible Oxidation of Early Earth

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