Supply of phosphate to early Earth by photogeochemistry after meteoritic weathering

Abstract

During terrestrial differentiation, the relatively small amount of phosphorus that migrated to the lithosphere was incorporated into igneous rock, predominantly in the form of basic calcium orthophosphate (Ca10(PO4)6(OH,F,Cl)2, apatite). Yet the highly insoluble nature of calcium apatite presents a significant problem to those contemplating the origin of life given the foundational role of phosphate (PO43−) in extant biology and the apparent requirement for PO43− as a catalyst, buffer and reagent in prebiotic chemistry. Reduced meteorites such as enstatite chondrites are highly enriched in phosphide minerals, and upon reaction with water these minerals can release phosphorus species of various oxidation states. Here, we demonstrate how reduced phosphorus species can be fully oxidized to PO43− simply by the action of ultraviolet light on H2S/HS. We used low-pressure Hg lamps to simulate ultraviolet output from the young Sun and 31P nuclear magnetic resonance spectroscopy to monitor the progress of reactions. Our experimental findings provide a cosmochemically and geochemically plausible means for supply of PO43− that was widely available to prebiotic chemistry and nascent life on early Earth and potentially on other planets.

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Fig. 1: Proposed photochemical synthesis of orthophosphate (PO43−).
Fig. 2: Photochemical oxidation of phosphite.
Fig. 3: Proposed mechanism for the formation of PSO33− and thence PO43− from the irradiation of H2PO2 and HS.
Fig. 4: Delivery of reduced phosphorus to Earth by late accretion.

Data availability

The authors declare that all data associated and supporting this study are available in the published article and Supplementary information. We have chosen not to make the data available in a publicly accessible repository at this time.

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Acknowledgements

The authors thank P. B. Rimmer for helpful discussions about atmospheric shielding from UV light and photochemical reactions and R. Brasser and O. Abramov for informative discussions about dynamical models and Earth’s formation. D.J.R. thanks T. Rutherford for assistance with NMR spectroscopy and C. Johnson for assistance with UV-Vis spectroscopy. This work was supported by the Medical Research Council (grant no. MC_UP_A024_1009 to J.D.S) and a grant from the Simons Foundation (grant no. 290362 to J.D.S.), and S.J.M. thanks the Collaborative for Research in Origins (CRiO) at the University of Colorado, which was supported by The John Templeton Foundation (principal investigator: S. Benner/FfAME): the opinions expressed in this publication are those of the authors and do not necessarily reflect the views of the John Templeton Foundation. S.J.M. also acknowledges the NASA Solar System Workings Program, grant 80NSSC17K0732 (principle investigator: O. Abramov/PSI).

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D.J.R. and J.D.S. designed the chemical experiments, D.J.R. carried out the chemical experiments, and D.J.R. and J.D.S. analysed the data. S.J.M. calculated the quantities of reduced phosphorus delivered to Earth from dynamical models. D.J.R. wrote the manuscript with input from J.D.S. and S.J.M. All authors read and approved the manuscript.

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Correspondence to Dougal J. Ritson or Stephen J. Mojzsis or John. D. Sutherland.

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Supplementary information

Supplementary Information

Supplementary Discussions 1–3, Note 1 and Figs. 1–18.

Supplementary Table 1

Table of mass productions for late accretion to Earth.

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Ritson, D.J., Mojzsis, S.J. & Sutherland, J.D. Supply of phosphate to early Earth by photogeochemistry after meteoritic weathering. Nat. Geosci. 13, 344–348 (2020). https://doi.org/10.1038/s41561-020-0556-7

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