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Native iron reduces CO2 to intermediates and end-products of the acetyl-CoA pathway
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Abstract
Autotrophic theories for the origin of life propose that CO 2 was the carbon source for primordial biosynthesis. Among the six known CO 2 fixation pathways in nature, the acetyl-CoA (AcCoA; or Wood-Ljungdahl) pathway is the most ancient, and relies on transition metals for catalysis. Modern microbes that use the AcCoA pathway typically fix CO 2 with electrons from H 2, which requires complex flavin-based electron bifurcation. This presents a paradox: how could primitive metabolic systems have fixed CO 2 before the origin of proteins? Here, we show that native transition metals (Fe 0, Ni 0 and Co 0) selectively reduce CO 2 to acetate and pyruvate-the intermediates and end-products of the AcCoA pathway-in near millimolar concentrations in water over hours to days using 1-40 bar CO 2 and at temperatures from 30 to 100 °C. Geochemical CO 2 fixation from native metals could have supplied critical C 2 and C 3 metabolites before the emergence of enzymes.
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“Second, Fe0, Ni0, Ni3Fe and silica‐supported Co‐Fe alloys can replace the proteins that synthesize formate, acetate, pyruvate from H2 and CO2 via the acetyl‐CoA pathway [60, 61, 62, 63, 64] (Fig. 1C).”
From Evidence for corrin biosynthesis in the last universal common ancestor (2025) · cites this paper as [61]
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“Moreover, only one of those seven, again only the acetyl CoA pathway, operates in vitro to form its main products – formate, acetate and pyruvate [49, 90] – from H2 and CO2 without enzymes or cofactors, using only metals or minerals that occur in hydrothermal vents as catalysts [60, 61, 62, 63, 64, 125].”
From Evidence for corrin biosynthesis in the last universal common ancestor (2025) · cites this paper as [61]
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“In fact, both the TCA and the WLP may have a non-enzymatic origin, testifying to their potential emergence long before LUCA (Ralser 2018;Varma et al. 2018).”
From The Emergence of Life (2019) · cites this paper as Varma et al. 2018
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“The fact that the oldest carbon fixation pathway known among organisms today, the acetyl-CoA pathway, uses H2 as an electron donor and CO2 as an electron acceptor, suggests that an acetyl-CoA-like pathway was present from the earliest stages [135,136,137] (Figure 4, step 1c).”
From ‘Whole Organism’, Systems Biology, and Top-Down Criteria for Evaluating Scenarios for the Origin of Life (2021) · cites this paper as [136]
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“the oldest carbon fixation pathway known among organisms today, the acetyl-CoA pathway [135,136], uses H2 as an electron donor and CO2 as an electron acceptor”
From ‘Whole Organism’, Systems Biology, and Top-Down Criteria for Evaluating Scenarios for the Origin of Life (2021) · cites this paper as [136]
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“In particular, the importance of relevant metals and metal clusters in the Hadean has settled in experimental work that recreates the origin of biochemistry in vitro, including carbon cycling [98,103,153], nitrogen fixation [154], ribosomal translation [155], and even the generation of pH gradients [156].”
From The Future of Origin of Life Research: Bridging Decades-Old Divisions (2020) · cites this paper as [153]
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“Pyruvate and glyoxylate have been shown to be accessible [140,141] by CO2 fixation through abiotic processes.”
From Prebiotic Reaction Networks in Water (2020) · cites this paper as [141]
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Metadata
- Authors
- Varma, S. J., Muchowska, K. B., Chatelain, P., & Moran, J.
- Affiliations
- Centre National de la Recherche Scientifique (FR)
- Corresponding author
- Moran, Joseph
- Venue
- Nature Ecology & Evolution
- Published
- 2018-04-23
- Volume
- 2
- Issue
- 6
- Pages
- 1019-1024
- ISSN
- 2397-334X (ISSN-L)
- PMC
- PMC5969571
- OpenAlex
- W2799784280
- Cited by
- 235
- References
- 53
- Citations by year
- 2026: 20 · 2025: 22 · 2024: 34 · 2023: 26 · 2022: 35 · 2021: 27 · 2020: 23 · 2019: 26 · 2018: 22
- FWCI
- 13.13
- Type
- journal article
- Language
- en
- Open access
- green
- doi.org
- Licence
- Locations
- Nature Ecology & Evolution (publishedVersion)
- bioRxiv (Cold Spring Harbor Laboratory) (acceptedVersion)
- PubMed (publishedVersion)
- Helmholtz Centre for Ocean Research Kiel (GEOMAR) (acceptedVersion)
- Europe PMC (PubMed Central) (acceptedVersion)
- PubMed Central (acceptedVersion)
- Funders
- European Commission (HORIZON2020)
- Agence Nationale de la Recherche (ANR-10-LABX-0026)
- Université de Strasbourg
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- acetyl-CoA pathway, CO2 fixation, native iron, metal catalysis, CO2 reduction, acetyl-CoA, origin of metabolism
- MeSH terms
- Acetyl Coenzyme A, Carbon Dioxide, Iron, Oxidation-Reduction
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