The New Avengers

Season 1, Episode 6: Target!

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In an attempt to break Steed's perfect shooting-range record, Purdey tackles the range with all her grace and skill. However, it's not enough as she misses one tiny percentage and gets hit with a mark. But other agents begin to die who have performed similarly, and Steed and Gambit start putting the clues together and find that they must work fast to save their friend and colleague before she succumbs to a nasty poison.