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You can use it once, for each time that Dark Valkyria is face-up on the field as an effect monster.

So imagine you have Dark Valkyria on the field, and you use its effect, then later it gets returned to hand, or flipped face-down. When you resummon it, after you switch on its gemini effect, you can use the counter effect once more.

It doesn't have to leave the field either, the same applies if it loses its effect. If a Normal Dark Valkyria is equipped with Supervise, you can activate the token effect. If Supervise is then removed, Dark Valkyria will revert back to being a Normal Monster (losing the token if it still has it) but if you then gemini summon it, you can activate the token effect once more.

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