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It seems kind of cutesy sounding to me. Like more of a nn, or a pet's name, even. :-/ I've mostly familiar with it as a nn for River (Calida here at BtN, and it was River Phoenix's nn as well--IIRC, one of his sisters named her son Rio after him). I'd have a bit of a hard time taking a man with the given name Rio seriously, I think. And I'd also have the Duran Duran song in my head, too. ;)

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Adding: Liberty Phoenix has a son named Rio Everest.