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In Captain America: Civil War, Bucky apparently can run as fast as enhanced Steve Rogers.

I don’t remember anything specific about how Bucky gets extra power beyond the bionic arm (which, I’m assumig is made of vibranium?).

What’s the story behind that? The serum that makes Steve Rogers better was only used once, the only prior being the Red Skull, right?

We do see, in that incident, the Winter Soldier steal 5 blue vials that created the death squad, but they were tested against Bucky initially who seems to already have some kind of enhancement.

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Whatever process Hydra used to gift Bucky with the abilities he has by Captain America: The Winter Soldier had already been started by Dr Arnim Zola when he was rescued from his lab in the Austrian Hydra Base by Rogers in Captain America: The First Avenger and was continued after his apparent death later in the film.

From "Marvel Cinematic Universe Wiki":

Using S.H.I.E.L.D.'s resources, Zola continued his experiments on Bucky Barnes with other doctors to turn him into HYDRA's secret weapon/assassin. Zola also managed to build an entire computer system which his mind was uploaded into as an artificially intelligent user interface. Though Zola's body died in 1972, his mind continued to live in cyberspace, where he was able to provide easy passage into the agency for HYDRA sleeper agents that either managed to escape justice during the war or were corrupted from within.

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  • What's interesting is we don't see the extent of Bucky's abilities until Captain America: Civil War, where he's running at the same speed as Capt America (chase scene with Black Panther in pursuit)
    – enorl76
    Oct 8, 2018 at 20:09

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