Methanol on the rocks: Green rust transformation promotes the oxidation of methane

10 July 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Shared coordination geometries between metal ions within reactive minerals and enzymatic metal cofactors hints at mechanistic and possibly evolutionary homology between particular abiotic chemical mineralogies and biological metabolism. The octahedral coordination of reactive Fe2+/3+ minerals such as green rusts, endemic to anoxic sediments and the early Earth’s oceans, mirrors the di-iron reaction center of soluble methane monooxygenase (sMMO), responsible for methane oxidation in methanotrophy. We show that methane oxidation occurs in tandem with the oxidation of green rust to lepidocrocite and magnetite, mimicking radical mediated methane oxidation found in sMMO to yield not only methanol but also halogenated hydrocarbons in the presence of seawater. This naturally occurring geochemical pathway for CH4 oxidation elucidates a previously unidentified carbon cycling mechanism in modern and ancient environments and reveals clues into mineral-mediated reactions in the synthesis of organic compounds necessary for the emergence of life.


Green rust
methane oxidation
origin of life

Supplementary materials

Supplementary text and figures
This document contains referenced data and graphs that was not included in the original manuscript.


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