leatherhat said:
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Samus at the end of Metroid Prime, 2002. Could be construed as blonde hair, but very obviously different.

The one on the right is Samus at the end of Metroid Fusion, 2002. Closer, but it still precedes the development of the Zero Suit, and she still has the non-anime face style. The Zero Suit again came in Zero Mission and Prime 2, both 2004, with the distinct Zero Suit face and such that has stuck with her.
EDIT:

Also here's her clear evolution through the Prime series

Monster Hunter: pissing me off since 2010.







