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This comes from a short backstage segment filmed before John Kerry's appearance on the show. It's fantastic hearing Colbert prepping Kerry about what he'll be like while he's in character. Colbert can be Borat-like in his perseverance to stay in character whenever he's on film.
The blonde moment is this one, in which Ms. South Carolina (pageant unknown) provides a truly stupid response to a question about Americans' inability to point out the USA on a world map. And was that Mario Lopez from Saved By The Bell hosting there? He kept a straight face with some difficulty, I see.