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Lightning-induced reduction of phosphorus oxidation state

Abstract

Phosphorus is frequently the limiting nutrient in marine and terrestrial ecosystems, largely owing to its poor solubility and slow movement through the rock cycle1,2. Phosphorus is viewed to exist in geological systems almost exclusively in its fully oxidized state as orthophosphate. However, many microorganisms use the partially oxidized forms—phosphite and hypophosphite—as alternative phosphorus sources3,4,5, and genomic evidence suggests that this selectivity is ancient6. Elucidating the processes that reduce phosphate is therefore key to understanding the biological cycling of phosphorus. Here we show that cloud-to-ground lightning reduces phosphate in lightning-derived glass compounds, termed fulgurites. We analysed the phosphorus chemistry of ten fulgurites retrieved from North America, Africa and Australia, using microprobes and 31P nuclear magnetic resonance. Half of the fulgurites contained reduced phosphorus, mainly in the form of phosphite. The amount and type of reduced phosphorus was dependent on the composition of the fulgurite section examined: carbon-rich sections contained around 22% reduced phosphorus in the form of iron phosphide, whereas other fulgurites contained between 37 and 68% in the form of phosphite. We suggest that lightning provides some portion of the reduced phosphorus used by microbes, and that phosphate reduction by lightning can be locally important to phosphorus biogeochemistry.

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Figure 1: 31P NMR spectra of fulgurite extracts.
Figure 2: Backscattered electron images of reduced-phosphorus carriers in fulgurites.
Figure 3: Oxygen fugacity diagram with phosphate–phosphite transition.

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Acknowledgements

This research was financially supported by grant NNX07AU08G from NASA Exobiology and Evolutionary biology. We thank D. Lauretta for use of laboratory space and equipment. Soil samples of York County, Pennsylvania, USA were provided by Ben Eiben, and La Paz County, Arizona, USA soil by T. Boswell of Joshua Tree Imports. The New South Wales Australia fulgurites were provided by A. Hutchison of Gemworx OZ.

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M.A.P. planned analyses, acquired and prepared samples, ran extractions and wrote the paper. K.B. prepared samples and acquired and analysed data.

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Correspondence to Matthew Pasek.

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Pasek, M., Block, K. Lightning-induced reduction of phosphorus oxidation state. Nature Geosci 2, 553–556 (2009). https://doi.org/10.1038/ngeo580

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