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The second season mainly focuses on the arrival of Elena's doppelgänger Katherine Pierce and the reasons she returned to Mystic Falls. The second season also introduces werewolves. Tyler's Uncle, Mason Lockwood, a werewolf, arrives in the town after the death of his brother, Tyler's father, and tells Tyler about the so called "Lockwood curse" that has run in their family for centuries. He tells Tyler that in order to activate the curse, more specifically to activate the "werewolf" gene, the person must kill someone. Katherine turns Caroline into a vampire so she can have a spy against Stefan and Elena, using Matt to scare Caroline into helping her. Caroline later tells Elena. Tyler accidentally kills an innocent girl after Katherine compelled her to make him angry. Katherine's main reason for returning to Mystic Falls was to find the moonstone, with the help of Mason, who is later killed by Damon. Katherine falls back on Plan B and calls in a favour from a witch to help her get the stone back from Stefan and Damon. The witch casts a spell on Elena and Katherine, meaning that when Katherine is hurt, it also affects Elena. When the witch finds out another Bennett is at the party and Katherine had deceived her, she puts a spell on the moonstone, injuring Katherine. Damon then leaves her in the original tomb, where he believes she belongs. She tells him the reason she hasn't killed Elena is because she has to protect her and she's in danger. Damon ignores her and leaves her screaming and crying in the tomb. Elena is later kidnapped, meaning Katherine was telling him the truth.

It is revealed that Elena isn't the only Petrova doppelgänger, but Katherine too, and maybe others. Elena needs to be sacrificed to break the sun and the moon curse, but she is rescued by Stefan and Damon. Klaus, the oldest vampire in history, is now hunting for her. Klaus wants to break the curse before the werewolves can do so.

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