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A plot enters your used pile the moment you physically reveal a new one. That means you will usually have 3 plots in your used pile when you reveal your 4th plot. When you reveal your last (usually 7th) plot, you do not return your used pile to your plot deck until after all the When Revealed abilities have resolved. That means The Doom of Valyria will successfully resolve in rounds 4, 5, 6 and 7 in normal circumstances. Abilities like Gulltown, Ricasso, or Lonely Hills would change this premise.
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Duplicates do not have the non-limited characteristic, so they will not be discarded. If a card has two duplicates and one is used to save it, the other duplicate will remain in play.
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Attachments are discarded in the same way as characters and locations. If attached character (or location) is also discarded by Doom, the cards are discarded simultaneously, so the attachment would not return to your hand. However, if a unique non-terminal attachment is duped, you can use the duplicate to save it, which will cause it to return to your hand when attached character (or location) leaves play.
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If you have fewer than 3 cards in hand, you cannot cancel the effect. If you physically have 3 or more cards in hand but are considered to have fewer than 3 due to Qartheen Galleas, you cannot fulfill the condition of discarding a hand of at least 3 cards.
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In a Melee game, the choice whether to cancel the effect is made by each opponent in player order.