As I've predicted elsewhere, if this series ends up going as dark as some people seem to expect, Sayaka will likely be the first main character to die. Her death will jolt Madoka awake to the reality of magical girls and the situation she'll have put herself in. For maximum angst, Sayaka will turn into a witch and Madoka will be forced to kill her.
The dramatic cues are there. I think the only thing that can save Sayaka will be the series not turning dark enough to kill off the girls in the first place.
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