Web's Boom, Headshot to Simon Gunther in "New Girl in Town", and the revelation of his Batman Gambit: he knew Rebecca would disobey orders, he put her on the wrong train and pulled tactical support, knowing Gunther would have overheard his dismissal of Rebecca and thus, she'd be alone. And thus a Magnificent Bastard was formed.
Rebecca's angry speech to Paul in "Old Wounds":
Rebecca: Becky George was a ten-year-old girl taken from her bed in the middle of the night by a stranger. Becky George was lost for eighteen months. Becky George got away on her own. No one found Becky George.
Rebecca: Rebecca! I'm Rebecca. And I am a special agent with the Federal Bureau of Investigation. I am not some lost little girl. Don't you ever presume to treat me like one.
Rebecca on the phone with the suicide hotline in "The Loneliest Number", trying to bait a suspect. She hides her face and sounds for all the world like she's sobbing and depressed, then hangs up the phone and turns completely calm and dry eyes up to Paul. Who's Web's Magnificent Bitch-in-training?
Danny bashing the car window open in "Declawed" to get to unsub. He does it without even batting an eyelash.