Photoshop Question

Hi!
I know this is not an Icon, but I'm really, really interested in this effect...
I just found this picture in a german rpg and the color effect fascinated me.





Does anyone know how to get such an coloring? I don't mean the green eyes, the brushes or the lines, but the shadows around Bonnie's face for example under the hair... And how do you get a picture with so less shades in the face?