Headshot

Remote strobe, off axis and above on camera right. Sunlight in front and to camera left acting as second key.
-2 stops ambient (so the strobe can fill)
+2 stops strobe exposure compensation (purposefully slightly over-exposed)
ISO 100
135mm @ ƒ2
1/30th of a second exposure (hand held)

Full Frame

Adjustments:
Contrast
Colour Contrast
Spot dodging (under left eye, mouth)