Biological carbon precursor to diagenetic siderite with spherical structures in iron formations
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During deposition of Precambrian iron formation, the combined sedimentation of ferrihydrite and phytoplankton biomass should have facilitated Fe(III) reduction during diagenesis. However, the only evidence for this reaction in iron formations is the iron and carbon isotope values preserved in the authigenic ferrous iron-containing minerals. Here we show experimentally that spheroidal siderite, which is preserved in many iron formation and could have been precursor to rhombohedral or massive siderite, forms by reacting ferrihydrite with glucose (a proxy for microbial biomass) at pressure and temperature conditions typical of diagenesis (170 °C and 1.2 kbar). Depending on the abundance of siderite, we found that it is also possible to draw conclusions about the Fe(III):C ratio of the initial ferrihydrite-biomass sediment. Our results suggest that spherical to rhombohedral siderite structures in deep-water, Fe-oxide iron formation can be used as a biosignature for photoferrotrophy, whereas massive siderite reflects high cyanobacterial biomass loading in highly productive shallow-waters.
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Some siderite formed during diagenetic and subsequent metamorphic oxidation of microbial biomass to CO2/bicarbonate coupled to reduction of Fe(III), followed by reaction of Fe2+aq with sediment pore-water bicarbonate.
“Such features suggest that some siderite formed during the diagenetic (biological or non-biological), and subsequent metamorphic, oxidation of microbial biomass to CO2/bicarbonate coupled to the reduction of Fe(III), followed by reaction of the product Fe 2+ aq with sediment pore-water bicarbonate (Johnson et al., 2008; Heimann et al., 2010; Köhler et al., 2013; Halama et al., 2016).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Köhler et al., 2013
The spheroidal forms of siderite found in several IFs are similar to those of the siderite grains formed experimentally when ferrihydrite is reacted with organic carbon at pressure and temperature conditions commensurate with IF diagenesis.
“For instance, the spheroidal forms of siderite found in several IFs are similar to those of the siderite grains formed experimentally when ferrihydrite is reacted with organic carbon at pressure and temperature conditions commensurate with IF diagenesis (Köhler et al., 2013).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Köhler et al., 2013
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“2 kbar for 14 days, formed mineral phases such as siderite, hematite, and magnetite (Köhler et al. 2013; Posth et al. 2013).”
BackgroundGroundwater table fluctuations recorded in zonation of microbial siderites from end-Triassic strata
Weibel, R., Lindström, S., Pedersen, G. K., et al. (2016) · Sedimentary Geology · doi:10.1016/j.sedgeo.2016.06.009 · Cited by 30 · see citing works
Limited Zn and Ni mobility during simulated iron formation diagenesis
Robbins, L. J., Swanner, E. D., Lalonde, S. V., Eickhoff, M., Paranich, M. L., Reinhard, C. T., Peacock, C. L., Kappler, A., & Konhauser, K. O. (2015) · Chemical Geology · doi:10.1016/j.chemgeo.2015.02.037 · Cited by 29 · see citing works
Sedimentology and geochemistry of Archean silica granules
Trower, E. J., Lowe, D. R., Zentner, D., & Fischer, W. W. (2015) · Geological Society of America Bulletin · doi:10.1130/b31181.1 · Cited by 29 · see citing works
“…augmented the emerging view that the deposition of mud-, silt-, and sand-sized chemical sand grains composed of silica (Stefurak et al., 2014), iron silicates (Rasmussen et al., 2013), and siderite (Köhler et al., 2013) was involved in the deposition of early Precambrian cherts and iron formations.”
BackgroundZhang, B., Fei, Y., Diao, M., et al. (2025) · Environmental Science & Technology · doi:10.1021/acs.est.4c11605 · Cited by 27 · see citing works
The Palaeoproterozoic Hotazel BIF-Mn Formation as an archive of Earth's earliest oxygenation
Mhlanga, X., Tsikos, H., Lee, B., Rouxel, O. J., Boyce, A. C., Harris, C., & Lyons, T. W. (2023) · Earth-Science Reviews · doi:10.1016/j.earscirev.2023.104389 · Cited by 28 · see citing works
A biological switch at the ocean surface as a cause of laminations in a Precambrian iron formation
HASHIZUME, K., Pinti, D. L., Orberger, B., Cloquet, C., Jayananda, M., & SOYAMA, H. (2016) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2016.04.023 · Cited by 26 · see citing works
Fadel, A., Lepot, K., Busigny, V., Addad, A., & Troadec, D. (2017) · Precambrian Research · doi:10.1016/j.precamres.2017.07.003 · Cited by 27 · see citing works
Rasmussen, B., Muhling, J. R., & Fischer, W. W. (2021) · Astrobiology · doi:10.1089/ast.2020.2376 · Cited by 24 · see citing works
“…1965; Cloud, 1965; Awramik and Barghoorn, 1977; Knoll et al., 1978; Strother and Tobin, 1987; Lanier, 1989; Moreau and Sharp, 2004; De Gregorio et al., 2009; Planavsky et al., 2009; Wacey et al., 2012; Ko¨hler et al., 2013; Shapiro and Konhauser, 2015; Alleon et al., 2016; Lepot et al., 2017).”
A one-million-year isotope record from siderites formed in modern ferruginous sediments
Vuillemin, A., Mayr, C., Schuessler, J. A., Friese, A., Bauer, K. W., Lücke, A., Heuer, V. B., Glombitza, C., Henny, C., von Blanckenburg, F., et al. (2022) · Geological Society of America Bulletin · doi:10.1130/b36211.1 · Cited by 23 · see citing works
Microbial biosignatures in ancient deep‐sea hydrothermal sulfides
Runge, E., Mansor, M., Kappler, A. A., & Duda, J. (2022) · Geobiology · doi:10.1111/gbi.12539 · Cited by 25 · see citing works
“For instance, magnetite can form during diagenesis or low- grade metamorphism via thermochemical reduction of primary Fe oxyhydroxides such as ferrihydrite and lepidocrocite with sedimentary organic matter (Halama et al., 2016; Köhler et al., 2013; Posth et al., 2013, 2014).”
BackgroundExperimental maturation of Archaea encrusted by Fe-phosphates
Miot, J., Bernard, S., Bourreau, M., Guyot, F., & Kish, A. (2017) · Scientific Reports · doi:10.1038/s41598-017-17111-9 · Cited by 20 · see citing works
Schad, M., Byrne, J. M., ThomasArrigo, L. K., Kretzschmar, R., Konhauser, K. O., & Kappler, A. A. (2022) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2022.05.016 · Cited by 19 · see citing works
Akinlotan, O. O. (2017) · Geological Magazine · doi:10.1017/s0016756817001017 · Cited by 19 · see citing works
Duverger, A., Bernard, S., Viennet, J., Miot, J., & Busigny, V. (2021) · Geochemistry Geophysics Geosystems · doi:10.1029/2021gc010056 · Cited by 18 · see citing works
“However, it is commonly assumed that such shortterm high-temperature conditions roughly approximate long-term lower-temperature conditions, making them appropriate conditions to mimic burial diagenesis processes (Alleon et al., 2017; Alleon, Bernard, Le Guillou, Daval, et al., 2016; Bernard et al., 2015; Beveridge et…”
BackgroundRobbins, L. J., Konhauser, K. O., Warchola, T. J., Homann, M., Thoby, M., Foster, I. S., Mloszewska, A. M., Alessi, D. S., & Lalonde, S. V. (2019) · Chemical Geology · doi:10.1016/j.chemgeo.2018.12.036 · Cited by 18 · see citing works
Goodwin, A., & Papineau, D. (2021) · Astrobiology · doi:10.1089/ast.2021.0010 · Cited by 16 · see citing works
“9E) in association with OM suggest that OM was diagenetically oxidized with ferric Fe, a process known to produce ferrous Fe in abiotic spheroids and microbial precipitates (Ko¨hler et al. , 2013; Picard et al. , 2015).”
Tong, X., Wang, C., Peng, Z., Li, Y., Hao, W., Mänd, K., Robbins, L. J., Zhang, L., Ke, Q., Zhai, M., et al. (2021) · Economic Geology · doi:10.5382/econgeo.4841 · Cited by 17 · see citing works
Origin of ooids, peloids and micro-oncoids of marine ironstone deposits in Western Siberia (Russia)
Rudmin, M. A., Banerjee, S., Maximov, P. N., et al. (2022) · Journal of Asian Earth Sciences · doi:10.1016/j.jseaes.2022.105361 · Cited by 16 · see citing works
Fischel, M. H. H., Clarke, C. E., & Sparks, D. L. (2023) · Geoderma · doi:10.1016/j.geoderma.2022.116305 · Cited by 16 · see citing works
Kovalick, A., Heard, A., Johnson, A. C., Chan, C. S., Ootes, L., Nielsen, S. G., Dauphas, N., Weber, B., & Bekker, A. (2024) · Geobiology · doi:10.1111/gbi.70003 · Cited by 3 · see citing works
“While diagenetic models have been proposed for granule formation in GIFs (Köhler et al. 2013; Dodd et al. 2018), the oolitic texture of the Gibraltar Formation GIF is reminiscent of that observed in carbonate ooid cortices that formed in wave-agitated environments (Trower, Lamb, and Fischer 2017).”
Heard, A. W., Dauphas, N., Hinz, I. L., Johnson, J. E., Blanchard, M., Alp, E. E., Hu, M. Y., Zhao, J. Y., Lavina, B., Fornace, M. E., et al. (2023) · ACS Earth and Space Chemistry · doi:10.1021/acsearthspacechem.2c00313 · Cited by 14 · see citing works
Liu, J., Zhang, Y., Shi, X., Chen, A., Tang, D., & Yang, T. (2023) · Palaeontology · doi:10.1111/pala.12685 · Cited by 12 · see citing works
Phosphate remobilization from banded iron formations during metamorphic mineral transformations
Schad, M., Halama, M., Jakus, N., Robbins, L. J., Warchola, T. J., Tejada, J., Kirchhof, R., Lalonde, S. V., Swanner, E. D., Planavsky, N. J., et al. (2021) · Chemical Geology · doi:10.1016/j.chemgeo.2021.120489 · Cited by 13 · see citing works
“As a comparison to more recalcitrant organic carbon, and consistent with previous low-grade metamorphism studies (Halama et al., 2016; Köhler et al., 2013; Posth et al., 2013; Robbins et al., 2015), we mixed ferrihydrite with glucose as a proxy for labile Corg (Clab).”
BackgroundMethodResultInfluentialThe biogeochemical iron cycle and astrobiology
Schröder, C. A., Köhler, I., Muller, F. L. L., Chumakov, A. I., Kupenko, I., Rüffer, R., & Kappler, A. A. (2016) · Hyperfine Interactions · doi:10.1007/s10751-016-1289-2 · Cited by 12 · see citing works
Han, X., Tomaszewski, E. J., Schoenberg, R., Konhauser, K. O., Amor, M., Pan, Y., Warter, V., Kappler, A. A., & Byrne, J. M. (2021) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2021.117052 · Cited by 12 · see citing works
“Similarly, studies that applied pressure-temperature (P/T) burial simulations of ferrihydrite mixed with dead microbial biomass or glucose (as a proxy for biomass) showed that magnetite in BIFs could also have formed by thermochemical Fe(III) reduction under low P/T metamorphic conditions (Halama et al., 2016; Kohler…”
BackgroundSun, L., Lechte, M. A., Shi, X., Zhou, X., Zhou, L., Fang, H., Xie, B., Wu, M., & Tang, D. (2021) · American Mineralogist · doi:10.2138/am-2022-7981 · Cited by 12 · see citing works
Li, Y., SUTHERLAND, B. R., Gingras, M. K., Owttrim, G. W., & Konhauser, K. O. (2021) · Journal of Sedimentary Research · doi:10.2110/jsr.2020.114 · Cited by 11 · see citing works
“…deposition process shown here will contribute to the explanation of the origin of both the common secondary iron minerals in BIF, such as siderite (FeCO3) (Köhler et al. 2013) or magnetite (Li et al. 2013), as well as the low organic-carbon contents preserved in BIF (Gole and Klein 1981).”
BackgroundTan, J., Ma, X., Hua, S., Ma, X., Wang, B., Zhang, B., Tian, W., Jiang, S., & Hu, R. (2024) · Energy & Fuels · doi:10.1021/acs.energyfuels.4c02127 · Cited by 11 · see citing works
Rudmin, M. A., Banerjee, S., Синкина, Е. А., Ruban, A., Kalinina, N., & Smirnov, P. (2022) · Marine and Petroleum Geology · doi:10.1016/j.marpetgeo.2022.105777 · Cited by 10 · see citing works
Silica botryoids from chemically oscillating reactions and as Precambrian environmental proxies
Varkouhi, S., & Papineau, D. (2023) · Geology · doi:10.1130/g50948.1 · Cited by 10 · see citing works
Deposition and termination of Neoproterozoic iron formations (NIFs): New insights from NIFs in China
Ye, H., Wu, C., Li, W., Lei, R., Sun, X., Hao, W., & Konhauser, K. O. (2024) · Earth-Science Reviews · doi:10.1016/j.earscirev.2024.104861 · Cited by 9 · see citing works
Rothwell, K. A., ThomasArrigo, L. K., Kaegi, R., & Kretzschmar, R. (2024) · Environmental Science Processes & Impacts · doi:10.1039/d4em00363b · Cited by 11 · see citing works
“70 Following oxidation in the absence of LMWOAs, the material transformed into small ( ∼ 200 nm) particles consistent with ferrihydrite aggregates 71 (Fig.”
Tong, X., Mänd, K., Li, Y., Zhang, L., Peng, Z., Wu, Q., Li, P., Zhai, M., Robbins, L. J., Wang, C., et al. (2021) · Minerals · doi:10.3390/min11010094 · Cited by 9 · see citing works
Bosco-Santos, A., Gilhooly, W., de Melo-Silva, P., Fouskas, F., Bouyon, A., Motta, J., Baldim, M. R., Fabricio-Silva, W., Philippot, P., & Oliveira, E. (2021) · Geoscience Frontiers · doi:10.1016/j.gsf.2021.101250 · Cited by 9 · see citing works
Rasmussen, B., & Muhling, J. R. (2020) · Geology · doi:10.1130/g47410.1 · Cited by 9 · see citing works
Effect of a giant meteorite impact on Paleoarchean surface environments and life
Drabon, N., Knoll, A. H., Lowe, D. R., Bernasconi, S. M., Brenner, A. R., & Mucciarone, D. A. (2024) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.2408721121 · Cited by 9 · see citing works
“Additional siderite may have formed during early metamorphism through the reaction of Fe oxyhydroxides with organic matter (94, 95).”
BackgroundSilva, G. G., Vincenzi, R. A., de Araujo, G. G., Venceslau, S. J. S., & Rodrigues, F. (2024) · Scientific Reports · doi:10.1038/s41598-024-64246-7 · Cited by 7 · see citing works
“This mineral is associated with biogeochemical cycles and is found in different contexts, such as past depositions of banded iron formations (BIF) or marine sedimentation zones, occurring in connection with potential biosignatures 33 , Vuillemin et al. 34 .”
BackgroundLi, Y., SUTHERLAND, B. R., Ilin, A. M., Schad, M., Robbins, L. J., Kappler, A. A., Yusta, I., Sánchez‐España, J., Owttrim, G. W., Dreher, C., et al. (2024) · South African Journal of Geology · doi:10.25131/sajg.127.0010 · Cited by 7 · see citing works
Dreher, C., Schad, M., Duda, J., Fischer, S., Shuster, J., Li, Y., Konhauser, K. O., & Kappler, A. A. (2025) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2025.07.023 · Cited by 7 · see citing works
An overview of experimental simulations of microbial activity in early Earth
Zhao, M., Zhao, Y., Lin, W., & Xiao, K. (2023) · Frontiers in Microbiology · doi:10.3389/fmicb.2022.1052831 · Cited by 7 · see citing works
“Calculations based on the results of microbial experiments suggest that the anoxygenic photoautotrophic bacteria could account for the formation of most, if not all, of the initial iron minerals in BIF (Kappler et al., 2005).”
BackgroundInfluentialSchmitt, L., Kirnbauer, T., Angerer, T., Volkmann, R., Владимирович, Р. В., Wirth, R., & Klein, S. (2023) · Mineralium Deposita · doi:10.1007/s00126-023-01218-3 · Cited by 6 · see citing works
“Therefore, siderite likely formed either via abiotic or biotic iron reduction during diagenesis (Heimann et al. 2010; Köhler et al. 2013) or by reduction of Fe during metamorphism (Halama et al. 2016).”
Hofmann, A. (2024) · Precambrian Research · doi:10.1016/j.precamres.2024.107584 · Cited by 6 · see citing works
Past and present dynamics of the iron biogeochemical cycle
Dauphas, N., Heard, A. W., Rêgo, E. S., Rouxel, O. J., Marin‐Carbonne, J., Pasquier, V., Bekker, A., & Rowley, D. B. (2024) · Elsevier eBooks · doi:10.1016/b978-0-323-99762-1.00059-0 · Cited by 7 · see citing works
From Precambrian Iron-Formation to Terraforming Mars: The JIMES Expedition to Santorini
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Multi-Element Imaging of a 1.4 Ga Authigenic Siderite Crystal
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“The simultaneous presence of organic matter and iron sulfide suggests some heterotrophic sulfate-reducing bacterial activity, while the iron carbonate may have formed either via microbial or thermal iron reduction (Hendry et al. 2000; Bernard et al. 2007; Koehler et al. 2013; Posth et al. 2013).”
Apatite and magnetite as probes into dissimilatory iron reduction in banded iron formations
Hu, T., Robbins, L. J., Konhauser, K. O., Liu, L., Bishop, B., Chi, G., & Xu, L. (2025) · Chemical Geology · doi:10.1016/j.chemgeo.2025.122676 · Cited by 6 · see citing works
Metal-driven anaerobic oxidation of methane and the Sturtian deglaciation
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“Their formation is attributed to multiple Fe 2+ oxidation pathways, including reaction with molecular oxygen (O 2 ) from oxygenic photosynthesis, photoferrotrophy, and microaerophilic chemolithoautotrophic bacterial oxidation 22,24 .”
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“…that, in the presence of Fe 3 + , organic matter can undergo thermal decomposition, produce CO 2 and serve as an electron donor under conditions of more than 170 ° C and 1.2 kPa, generally during burial diagenesis when Fe 3 + is reduced to Fe 2 + (K ¨ ohler et al ., 2013; Halama et al ., 2016).”
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Iron and phosphorus cycling under ferruginous conditions
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- Authors
- Köhler, I., Konhauser, K. O., Papineau, D., Bekker, A., & Kappler, A.
- Affiliations
- University of Tübingen (DE)
- University of Alberta (CA)
- Boston College (US)
- University of Manitoba (CA)
- Corresponding author
- Kappler, Andreas
- Venue
- Nature Communications
- Published
- 2013-04-23
- Volume
- 4
- Issue
- 1
- Pages
- 1741-1741
- ISSN
- 2041-1723 (ISSN-L)
- OpenAlex
- W2168396934
- Semantic Scholar
- b00abed767286f0fd4edba1de6f89bc10ac4c837
- Cited by
- 123
- References
- 49
- Citations by year
- 2026: 6 · 2025: 9 · 2024: 16 · 2023: 11 · 2022: 8 · 2021: 15 · 2020: 5 · 2019: 4 · 2018: 5 · 2017: 13 · 2016: 9 · 2015: 13 · 2014: 7 · 2013: 2
- FWCI
- 7.03
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Licence
- Locations
- Nature Communications (publishedVersion)
- PubMed (publishedVersion)
- RePEc: Research Papers in Economics (submittedVersion)
- Funders
- National Aeronautics and Space Administration (NNX08AO16G, NNA09DA81A, NNX12AG14G, NNA04CC09A)
- Boston College
- Carnegie Institution of Washington (NNA04CC09A)
- Deutsche Forschungsgemeinschaft (KA 1736/4-1)
- Natural Sciences and Engineering Research Council of Canada (NNA04CC09A, KA 1736/4-1)
- Geological Survey of Western Australia
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Keywords
- siderite, iron-formation, diagenesis, ferrihydrite, Fe(III) reduction, microbial biomarkers, glucose, Precambrian, cyanobacteria, deep-water sediments, shallow-water sediments
- MeSH terms
- Carbon, Carbonates, Ferric Compounds, Iron, Pressure, Silicon Dioxide, Temperature, Time Factors, Geologic Sediments, Geological Phenomena
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