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for three ages Melkor is a prisoner in the halls of Mandos, and after he meets Ungoliant, he remains in dark form ever after (cf. Of the darkening of Valinor, Silmarillion) - how then could he appear to Men in a "great and beautiful
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It is assumed that when Men appeared in Beleriand, it was many generations past their awakening. Therefore, Fall of Man happened before chaining of Melko.