The DOI matches its Crossref record; 52 of the 53 references it cites were found in a registry or an index.
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]
Experimental — accuracy not yet measuredThe source backs part of the claim, not all of it — or backs it for a different population, condition or comparison.
In the citing paper
“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]
In the citing paper
“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]
In the citing paper
“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]
In the citing paper
“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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Citations
Cites
Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting
Roger, I., Shipman, M. A., & Symes, M. D. (2017) · Nature Reviews Chemistry · doi:10.1038/s41570-016-0003 · Cited by 3,503
Before enzymes and templates: theory of surface metabolism
Wächtershäuser, G. (1988) · Microbiological Reviews · doi:10.1128/mmbr.52.4.452-484.1988 · Cited by 1,242
The physiology and habitat of the last universal common ancestor
Weiss, M. C., Sousa, F. L., Mrnjavac, N., Neukirchen, S., Roettger, M., Nelson-Sathi, S., & Martin, W. F. (2016) · Nature Microbiology · doi:10.1038/nmicrobiol.2016.116 · Cited by 1,049
Prebiotic Systems Chemistry: New Perspectives for the Origins of Life
Ruiz-Mirazo, K., Briones, C., & de la Escosura, A. (2014) · Chemical Reviews · doi:10.1021/cr2004844 · Cited by 930
Corrosion of Iron by Sulfate-Reducing Bacteria: New Views of an Old Problem
Enning, D., & Garrelfs, J. (2013) · Applied and Environmental Microbiology · doi:10.1128/aem.02848-13 · Cited by 921
Transient assembly of active materials fueled by a chemical reaction
Boekhoven, J., Hendriksen, W. E., Koper, G. J. M., Eelkema, R., & van Esch, J. H. (2015) · Science · doi:10.1126/science.aac6103 · Cited by 889
Molybdenum cofactors, enzymes and pathways
Schwarz, G., Mendel, R. R., & Ribbe, M. W. (2009) · Nature · doi:10.1038/nature08302 · Cited by 872
Schuchmann, K., & Müller, V. (2014) · Nature Reviews Microbiology · doi:10.1038/nrmicro3365 · Cited by 845
On the origin of biochemistry at an alkaline hydrothermal vent
Martin, W., & Russell, M. J. (2007) · Philosophical Transactions of the Royal Society B: Biological Sciences · doi:10.1098/rstb.2006.1881 · Cited by 771
Alternative Pathways of Carbon Dioxide Fixation: Insights into the Early Evolution of Life?
Fuchs, G. (2011) · Annual Review of Microbiology · doi:10.1146/annurev-micro-090110-102801 · Cited by 726
Beyond the Calvin Cycle: Autotrophic Carbon Fixation in the Ocean
Hügler, M., & Sievert, S. M. (2010) · Annual Review of Marine Science · doi:10.1146/annurev-marine-120709-142712 · Cited by 721
Autotrophic carbon fixation in archaea
Berg, I. A., Kockelkorn, D., Ramos-Vera, W. H., Say, R. F., Zarzycki, J., Hügler, M., Alber, B. E., & Fuchs, G. (2010) · Nature Reviews Microbiology · doi:10.1038/nrmicro2365 · Cited by 719
Activated Acetic Acid by Carbon Fixation on (Fe,Ni)S Under Primordial Conditions
Huber, C., & Wächtershäuser, G. (1997) · Science · doi:10.1126/science.276.5310.245 · Cited by 714
Can, M., Armstrong, F. A., & Ragsdale, S. W. (2014) · Chemical Reviews · doi:10.1021/cr400461p · Cited by 625
Experimental evidence for the existence of iron-rich metal in the Earth's lower mantle
Frost, D. J., Liebske, C., Langenhorst, F., McCammon, C. A., Trønnes, R. G., & Rubie, D. C. (2004) · Nature Cell Biology · doi:10.1038/nature02413 · Cited by 612
A new ferredoxin-dependent carbon reduction cycle in a photosynthetic bacterium.
Evans, M. C. W., Buchanan, B. B., & Arnon, D. I. (1966) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.55.4.928 · Cited by 582
H 2 -rich fluids from serpentinization: Geochemical and biotic implications
Sleep, N. H., Meibom, A., Fridriksson, T., Coleman, R. G., & Bird, D. K. (2004) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0405289101 · Cited by 568
Primordial Carbonylated Iron-Sulfur Compounds and the Synthesis of Pyruvate
Cody, G. D., Boctor, N. Z., Filley, T. R., Hazen, R. M., Scott, J. H., Sharma, A., & Yoder, H. S. (2000) · Science · doi:10.1126/science.289.5483.1337 · Cited by 441
Universality in intermediary metabolism
Smith, E., & Morowitz, H. J. (2004) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0404922101 · Cited by 408
Energy conservation via electron-transferring flavoprotein in anaerobic bacteria
Herrmann, G., Jayamani, E., Mai, G., & Buckel, W. (2008) · Journal of Bacteriology · doi:10.1128/jb.01422-07 · Cited by 407
The origin of intermediary metabolism
Morowitz, H. J., Kostelnik, J. D., Yang, J. J., & Cody, G. D. (2000) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.110153997 · Cited by 338
Bacterial Methanogenesis and Growth from CO 2 with Elemental Iron as the Sole Source of Electrons
Daniels, L., Belay, N., Rajagopal, B. S., & Weimer, P. J. (1987) · Science · doi:10.1126/science.237.4814.509 · Cited by 287
The Implausibility of Metabolic Cycles on the Prebiotic Earth
Orgel, L. E. (2008) · PLoS Biology · doi:10.1371/journal.pbio.0060018 · Cited by 271
Classification of Meteorites and Their Genetic Relationships
Krot, A. N., Keil, K., SCOTT, E. R. D., Goodrich, C. A., & WEISBERG, M. K. (2013) · Elsevier eBooks · doi:10.1016/b978-0-08-095975-7.00102-9 · Cited by 271
Abiotic methane formation during experimental serpentinization of olivine
McCollom, T. M. (2016) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1611843113 · Cited by 241
Metals promote sequences of the reverse Krebs cycle
Muchowska, K. B., Varma, S. J., Chevallot-Beroux, E., Lethuillier-Karl, L., Li, G., & Moran, J. (2017) · Nature Ecology & Evolution · doi:10.1038/s41559-017-0311-7 · Cited by 228
Self-citationBio-inspired CO 2 conversion by iron sulfide catalysts under sustainable conditions
Roldán, A., Hollingsworth, N., Roffey, A., Islam, H.-U., Goodall, J. B. M., Catlow, C. R. A., Darr, J. A., Bras, W., Sankar, G., Holt, K. B., et al. (2015) · Chemical Communications · doi:10.1039/c5cc02078f · Cited by 226
Opinion: Studies on the origin of life — the end of the beginning
Sutherland, J. D. (2017) · Nature Reviews Chemistry · doi:10.1038/s41570-016-0012 · Cited by 225
The Origin and Nature of Life on Earth: The Emergence of the Fourth Geosphere
Smith, E., & Morowitz, H. J. (2016) · doi:10.1017/cbo9781316348772 · Cited by 215
Furdui, C., & Ragsdale, S. W. (2000) · Journal of Biological Chemistry · doi:10.1074/jbc.m003291200 · Cited by 214
Metal availability and the expanding network of microbial metabolisms in the Archaean eon
Moore, E. K., Jelen, B. I., Giovannelli, D., Raanan, H., & Falkowski, P. G. (2017) · Nature Geoscience · doi:10.1038/ngeo3006 · Cited by 204
An origin-of-life reactor to simulate alkaline hydrothermal vents
Herschy, B., Whicher, A., Camprubi, E., Watson, C., Dartnell, L., Ward, J., Evans, J. R. G., & Lane, N. (2014) · Journal of Molecular Evolution · doi:10.1007/s00239-014-9658-4 · Cited by 194
The Emergence and Early Evolution of Biological Carbon-Fixation
Braakman, R., & Smith, E. (2012) · PLoS Computational Biology · doi:10.1371/journal.pcbi.1002455 · Cited by 173
Kato, S., Yumoto, I., & Kamagata, Y. (2014) · Applied and Environmental Microbiology · doi:10.1128/aem.02767-14 · Cited by 158
The Compositional and Evolutionary Logic of Metabolism
Braakman, R., & Smith, E. (2012) · Physical Biology · doi:10.1088/1478-3975/10/1/011001 · Cited by 158
Iron catalysis at the origin of life
Camprubi, E., Jordan, S. F., Vasiliadou, R., & Lane, N. (2017) · IUBMB Life · doi:10.1002/iub.1632 · Cited by 144 · cited 3×
“…forms of the rTCA cycle may have once been united with the acetyl CoA pathway in an ancestral, possibly prebiotic, carbon fixation network.13,24,33,34 While these proposals provide strong explanatory power for the structure of extant metabolism, supporting chemical evidence is critically…”
Cody, G. D., Boctor, N. Z., Hazen, R. M., Brandes, J. A., Morowitz, H. J., & Yoder, H. S. (2001) · Geochimica et Cosmochimica Acta · doi:10.1016/s0016-7037(01)00674-3 · Cited by 132
Cooper, G., Reed, C., Nguyen, D. T., Carter, M., & Wang, Y. (2011) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1105715108 · Cited by 131
A Mild Hydrothermal Route to Fix Carbon Dioxide to Simple Carboxylic Acids
He, C., Tian, G., Liu, Z., & Feng, S. (2010) · Organic Letters · doi:10.1021/ol9025414 · Cited by 116
Ljungdahl, L. G., Irion, E., & Wood, H. G. (1965) · Biochemistry · doi:10.1021/bi00888a030 · Cited by 108
Driving Parts of Krebs Cycle in Reverse through Mineral Photochemistry
Zhang, X. V., & Martin, S. T. (2006) · Journal of the American Chemical Society · doi:10.1021/ja066103k · Cited by 106
Sousa, F. L., & Martin, W. F. (2014) · Biochimica et Biophysica Acta (BBA) - Bioenergetics · doi:10.1016/j.bbabio.2014.02.001 · Cited by 100
Out of fuzzy chemistry: from prebiotic chemistry to metabolic networks
Peretó, J. (2012) · Chemical Society Reviews · doi:10.1039/c2cs35054h · Cited by 96
Iron and Stony-Iron Meteorites
Benedix, G. K., Haack, H., & McCoy, T. J. (2013) · Treatise on Geochemistry · doi:10.1016/b978-0-08-095975-7.00109-1 · Cited by 75
The Abiotic Chemistry of Thiolated Acetate Derivatives and the Origin of Life
Chandru, K., Gilbert, A. R., Butch, C. J., Aono, M., & Cleaves, H. J. (2016) · Scientific Reports · doi:10.1038/srep29883 · Cited by 67
On the Dissipation of Thermal and Chemical Energies on the Early Earth
Russell, M. J., Hall, A. J., & Mellersh, A. R. (2003) · Springer eBooks · doi:10.1007/978-94-017-0111-2_10 · Cited by 45
Native metals, electron bifurcation, and CO2 reduction in early biochemical evolution
Sousa, F. L., Preiner, M., & Martin, W. F. (2018) · Current Opinion in Microbiology · doi:10.1016/j.mib.2017.12.010 · Cited by 44
Ligand Field Theory and the Origin of Life as an Emergent Feature of the Periodic Table of Elements
Morowitz, H. J., Srinivasan, V., & Smith, E. (2010) · Biological Bulletin · doi:10.1086/bblv219n1p1 · Cited by 42
Reduction of aqueous CO2 at ambient temperature using zero-valent iron-based composites
Guan, G., Kida, T., Ma, T., Kimura, K., Abe, E., & Yoshida, A. (2003) · Green Chemistry · doi:10.1039/b304395a · Cited by 39
Trace elements in natural metallic iron from Disko Island, Greenland
Kl�ck, W., Palme, H., & Tobschall, H. J. (1986) · Contributions to Mineralogy and Petrology · doi:10.1007/bf00389387 · Cited by 38
Water, Air, Earth and Cosmic Radiation
Bassez, M.-P. (2015) · Origins of Life and Evolution of Biospheres · doi:10.1007/s11084-015-9402-0 · Cited by 17
Bassez, M. (2017) · Origins of Life and Evolution of Biospheres · doi:10.1007/s11084-017-9534-5 · Cited by 17
Research works printed but not linked: 1
- Darling, D. J. The Universal Book of Astronomy 260 (Wiley, Hoboken, 2004).
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Synthesis and breakdown of universal metabolic precursors promoted by iron
Muchowska, K. B., Varma, S. J., & Moran, J. (2019) · Nature · doi:10.1038/s41586-019-1151-1 · Cited by 365
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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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