Molecular hydrogen (H_2) is the second most abundant trace gas in the atmosphere after methane (CH_4). In the troposphere, the D/H ratio of H_2 is enriched by 120‰ relative to the world's oceans. This cannot be explained by the sources of H_2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H_2 from its single largest source—the photochemical oxidation of methane—has yet to be determined. Here we show that the D/H ratio of stratospheric H2 develops enrichments greater than 440‰, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H_2 produced from CH_4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H_2 from CH_4 concentrates D in the product H_2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H_2
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