I think it's heavily implied, at the very least, that Sakura was born with Ambrosia and always knew she had it (she did say she's always had Shakuntiira in her). And think of who she is and what her circumstances are.
Shierra got hers by drinking pure Mermaid blood which has Aquarius' power in it.
The Hasas High Priestess and the Dwaven princess were both likely born with it.
And I'm guessing priests or priestesses or the like have ways to detect since it's a sort of divine power.
Anyway, yeah, I think you're right about how Kai can sort this out.
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