If someone looks like a woman you're going to address that person as a woman. How they identify doesn't matter because that's not what I asked. Chromosomes and genitals are way down on the list of things you use as clues to identify someone as a man or a woman.
So in the real world you have no chance on basing your pronouns on sex because you can't possibly know it. As I've also already pointed out, there are biological women with Y chromosomes. It's rare but it happens.
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