Deuterium enrichment of interstellar methanol is reproduced experimentally for the first time via grain-surface H-D substitution in solid methanol at an atomic D/H ratio of 0.1. Although previous gas-grain models successfully reproduce the deuterium enrichments observed in interstellar methanol molecules (D/H of up to 0.4, compared to the cosmic ratio of ~10 -5 ), the models exclusively focus on deuterium fractionation resulting from the successive addition of atomic hydrogen/deuterium on CO. The mechanism proposed here represents a key route for deuterium enrichment that reproduces the high observed abundances of deuterated methanol, including multiple deuterations.
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