Huh. Come to think of it, Firefly really does have some almost-perfect exemplars of the alignments. I do disagree with some of that chart, though:

The Operative--I agree with the commenter who says he's Lawful Evil. Firebombing a civilian town leaves little doubt. Simon is probably a better fit for Lawful Neutral.

Saffron--She's not a psycho, she's just willing to do anything for her own personal profit, which is Neutral Evil in a nutshell. Besides, the Reapers Reavers are classic Chaotic Evil anyway.