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This will log you out of the main account you're using for TweetDeck. If you want to remove another account from your list, instead, go to "Accounts" in the navigation bar (the icon looks like two people). Click the down arrow on the account you want to leave, and then hit "Leave this team," followed by "Leave."

Summary:
Hit the cog icon in the navigation bar on the left side of the screen. Click "Log out". Confirm that you want to sign out by hitting "Log out".