Katniss lay flowers around Rue's body and gave her the District 12 sign of respec
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I think the moment she lays flowers on rue is where this shift takes place. There is now a greater cause that Katniss has entered into than merely her survival. Katniss makes sure that her display of grief over Rue carries a subtext of rebellion against the people she really holds responsible for Rue's murder. She now makes it clear that the Capitol and President Snow are her real enemies.