One of the things I like asking candidates is "Tell me about a time you screwed up so royally that you were sure you were getting fired." Let's be honest, we all have one or two.. and if you don't, then your one or two are coming. It's what you learned to do differently that I care about. And if you don't have one, you're either a) incredibly lucky, b) too new to the industry, or c) lying.
I asked similar, and agree that it's a really useful question.
I think it's an especially great one for startups, as successful candidates are more likely to come into contact with production systems.
For these positions you not only want people capable of recovering accidents, but also people who have screwed up because, conversely, they've been trusted not to screw up. Those who've never been trusted enough to not damage a system are unlikely to be of much use.