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Micronutrient availability in Precambrian oceans controlled by greenalite formation

Nature Geoscience volume 16, pages 1188–1193 (2023)Cite this article

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Abstract

Metabolisms that evolved in the Archaean era (4.0–2.5 billion years ago) preferentially selected iron, manganese and molybdenum to form metalloproteins, whereas the majority of zinc-, copper- and vanadium-binding proteins emerged much later. The initial preference for these elements is commonly interpreted to reflect their availability in anoxic seawater, with free sulfide proposed as a key influence. While sulfidic waters reduce the availability of zinc and copper, they also remove molybdenum and leave behind vanadium. Furthermore, current geochemical data reflect predominantly ferruginous (Fe2+-rich), rather than sulfidic, conditions. Consistent with this, recent sedimentological work has uncovered abundant iron silicate minerals in Archaean rocks. Here we quantify metal partitioning during the formation and subsequent diagenesis of an Fe(ii) silicate mineral, a precursor to crystalline greenalite, in both seawater and hot hydrothermal fluids. Our data show that Fe(ii) silicates could have precipitated rapidly in Archaean hydrothermal plumes, severely attenuating hydrothermal delivery of key nutrients, in particular copper, zinc and vanadium. These results provide a mechanistic explanation for metal availability patterns in Archaean oceans that is consistent with temporal patterns of metal utilization predicted from protein structures and comparative genomics. Further, our data suggest natural greenalite may provide an archive of metal availability in deep time.

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Fig. 1: Experimental data showing the relationship between the solubility and kinetics of Fe(ii) silicate precipitation with Fe2+, SiO2(aq.), pH and temperature52.
Fig. 2: Iron, silica and trace metal concentrations in solution during Fe(ii) silicate precipitation and calculated partition coefficients52.
Fig. 3: Schematic depiction of trace metal cycling during greenalite precipitation, diagenesis and burial.

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Data availability

A supplementary file containing experimental data is available online in the BGS data repository (https://doi.org/10.5285/c40cdd54-583a-43b2-b5fe-1784cbabfd71). Correspondence and requests for data or materials should be directed to the corresponding author.

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Acknowledgements

R.T. acknowledges financial support from NERC grant NE/M013014/1, NRF-DSIs CIMERA and GENUS and the BIOGRIP platform. We are grateful to N. Tosca for access to laboratory facilities and comments on an earlier version of this paper and to E. Tipper, M. Greaves and R. Hindshaw for assistance with ICP-OES analyses at the Department of Earth Science, University of Cambridge.

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Authors and Affiliations

  1. Department of Geological Sciences, University of Cape Town, Cape Town, South Africa

    Rosalie Tostevin

  2. Department of Earth Science, University of Oxford, Oxford, UK

    Rosalie Tostevin & Imad A. M. Ahmed

  3. Nanolyse Technologies, London, UK

    Imad A. M. Ahmed

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R.T. designed the study, performed the experiments and analysed the results. I.A.M.A. and R.T. acquired synchrotron data, and I.A.M.A. modelled the results. R.T. wrote the paper with input from I.A.M.A.

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Correspondence to Rosalie Tostevin.

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Nature Geoscience thanks Romain Guilbaud, Elizabeth Swanner and Jena Johnson for their contribution to the peer review of this work. Primary Handling Editor: James Super, in collaboration with the Nature Geoscience team.

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Tostevin, R., Ahmed, I.A.M. Micronutrient availability in Precambrian oceans controlled by greenalite formation. Nat. Geosci. 16, 1188–1193 (2023). https://doi.org/10.1038/s41561-023-01294-0

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