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In the climax of Captain America: Civil War (2016), Zemo showed Iron Man how his parents really died, and that the Winter Soldier was responsible.

Afterwards, Iron Man asked Captain America whether he knew about it. Captain America admitted that, while he didn't know that Bucky (the Winter Soldier) was responsible, he did know that Howard and Maria's deaths weren't accidental.

But how? How did Captain America know the truth behind Iron Man's parents' death? How did he know that it was not an accident, but murder? This incident happened on 16 December 1991, and Captain America was buried in ice at that time. Did anyone tell him after he awoke? Am I missing something here?

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You have to refer to Captain America: Winter Soldier movie for that. In that movie, Arnim Zola tells to Cap about how Hydra infiltrated S.H.I.E.L.D and during that sequence, Zola says that Howard Stark's death was not an accident.

For source check this video of the scene:

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    Is this the only way Steve Rogers knows anything Tony Stark’s parents deaths? In Civil War, he’s directly confronted by Tony, to ask if he knew Bucky was responsible... – enorl76 Oct 6 '18 at 14:32

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