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Isotopic constraints on lightning as a source of fixed nitrogen in Earth’s early biosphere

Nature Geoscience volume 16, pages 478–484 (2023)Cite this article

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Abstract

Bioavailable nitrogen is thought to be a requirement for the origin and sustenance of life. Before the onset of biological nitrogen fixation, abiotic pathways to fix atmospheric N2 must have been prominent to provide bioavailable nitrogen to Earth’s earliest ecosystems. Lightning has been shown to produce fixed nitrogen as nitrite and nitrate in both modern atmospheres dominated by N2 and O2 and atmospheres dominated by N2 and CO2 analogous to the Archaean Earth. However, a better understanding of the isotopic fingerprints of lightning-generated fixed nitrogen is needed to assess the role of this process on early Earth. Here we present results from spark discharge experiments in N2−CO2 and N2−O2 gas mixtures. Our experiments suggest that lightning-driven nitrogen fixation may have been similarly efficient in the Archaean atmosphere, compared with modern times. Measurements of the isotopic ratio (δ15N) of the discharge-produced nitrite and nitrate in solution show very low values of −6‰ to −15‰ after equilibration with the gas phase with a calculated endmember composition of −17‰. These results are much lower than most δ15N values documented from the sedimentary rock record, which supports the development of biological nitrogen fixation earlier than 3.2 billion years ago. However, some Paleoarchean records (3.7 billion years ago) may be consistent with lightning-derived nitrogen input, highlighting the potential role of this process for the earliest ecosystems.

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Fig. 1: Measurements of δ15N in sedimentary rocks over geologic time, separated by metamorphic grade.
Fig. 2: Schematic of experimental set-up of the discharge experiment.
Fig. 3: Chemical pathways during spark discharge in N2−O2 and N2−CO2 gas mixtures.
Fig. 4: Energy yield of fixed nitrogen products.
Fig. 5: Nitrogen isotope ratios of aqueous nitrate and nitrite.

Data availability

A full methods section, a detailed description of the chemical processes, the description of additional experiments and a machine-readable table of the data presented in this work are available online. Access the data at https://doi.org/10.5285/81dfa4de-5a47-479f-8de8-15e5ef398072. Source data are provided with this paper.

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Acknowledgements

We thank H. Cleaves for technical advice on the experimental set-up, P. B. Rimmer and the members of the Leverhulme Centre for Life in the Universe (Cambridge) for helpful discussions of our results, and B. K. D. Pearce for comments on our paper. P.B. acknowledges a St Leonard’s Interdisciplinary Doctoral Scholarship from the University of St Andrews. E.E.S. acknowledges funding from a Royal Society research grant (RGS\R1\211184) and from a NERC Frontiers grant (NE/V010824/1). C.H. is part of the CHAMELEON MC ITN EJD, which received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement number 860470. To meet institutional and research funder open access requirements, any accepted paper arising shall be open access under a Creative Commons Attribution (CC BY) reuse licence with zero embargo.

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Authors and Affiliations

  1. Centre for Exoplanet Science, University of St Andrews, St Andrews, UK

    Patrick Barth, Eva E. Stüeken, Lukas Rossmanith & Mark Claire

  2. School of Earth & Environmental Sciences, University of St Andrews, St Andrews, UK

    Patrick Barth, Eva E. Stüeken, Yuqian Peng & Mark Claire

  3. SUPA, School of Physics & Astronomy, University of St Andrews, St Andrews, UK

    Patrick Barth & Lukas Rossmanith

  4. Space Research Institute, Austrian Academy of Sciences, Graz, Austria

    Patrick Barth & Christiane Helling

  5. Fakultät für Mathematik, Physik und Geodäsie, TU Graz, Graz, Austria

    Christiane Helling

  6. School of Chemistry, University of St Andrews, St Andrews, UK

    Lukas Rossmanith

  7. Institute at Brown for Environment and Society, Brown University, Providence, RI, USA

    Wendell Walters

  8. Department of Earth, Environmental and Planetary Sciences, Brown University, Providence, RI, USA

    Wendell Walters

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Contributions

E.E.S. and C.H. conceived the project; E.E.S. and P.B. built the experimental set-up; P.B., L.R. and Y.P. carried out the experiments; P.B., L.R., Y.P. and W.W. performed the analyses; M.C. provided analytical support; P.B., E.E.S., C.H. and W.W. analysed the data; P.B. wrote the paper with contributions from all authors.

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Correspondence to Patrick Barth.

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Nature Geoscience thanks Linda Godfrey, Jennifer Stern, Laurence Yeung and Ben Pearce for their contribution to the peer review of this work. Primary Handling Editors: Tamara Goldin and Rebecca Neely, in collaboration with the Nature Geoscience team.

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Selection of data used to produce Fig. 4.

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Barth, P., Stüeken, E.E., Helling, C. et al. Isotopic constraints on lightning as a source of fixed nitrogen in Earth’s early biosphere. Nat. Geosci. 16, 478–484 (2023). https://doi.org/10.1038/s41561-023-01187-2

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