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After leaving the KGB, Black Widow encountered Spider-Man in New York as she was trying to attract S.H.I.E.L.D.'s attention. Spider-Man thought he was saving Natasha, but she ended up knocking him out with her widow's bite and took his web shooters, giving them as a peace offering to Col. Fury, who recruited her into S.H.I.E.L.D.'s Shadow Team. There she worked with Clint Barton (aka Hawkeye) on a number of clandestine missions. Much of her past is a mystery, and it seems she has her share of secrets. Recently, with Quicksilver and Scarlet Witch joining the Shadow Team, Widow and Hawkeye were put on the public team, just in time for the Chitauri (Skrull) assault. Another of Widow's missions was to protect the President during Magneto's return from his brainwipe.
Shortly afterwards, Wolverine (accompanied by Spider-Man) confronted Natasha in her apartment when he was being chased by agents using his Weapon X file. She basically told him to get lost, and that she knew nothing about his problems.
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