Information about atmospheric conditions far back in Earth's history is embedded in the isotopic composition of fossil microbes. Such studies are technically demanding, but hold considerable promise.
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SHUHAI XIAO
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Mojzsis, S. Probing early atmospheres. Nature 425, 249–250 (2003). https://doi.org/10.1038/425249a
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DOI: https://doi.org/10.1038/425249a