The Aki Sisters, Minoriko Aki and Shizuha Aki:
As you already know, Shinto is a polytheistic religion. In fact, it's REALLY polytheist. There are countless gods, or "kami", of various shapes and sizes. 8 million gods is often used as a shorthand for how many there are. For that matter, the threshold for "godhood" is actually rather lower than most religions. There are gods of incredibly specific concepts.
In this case, the Aki sisters. Minoriko Aki is the one with the hat and apron and Shizuha Aki is the one without. Minoriko Aki is the younger one. They're gods of Autumn. Very specific parts of Autumn. Minoriko Aki is the more powerful of the two, being a god of agriculture and harvest. Shizuha, meanwhile... is the god of dead leaves. She turns leaves orange, red, and brown when fall comes around, and that's it. Truly someone capable of smiting you.
They both appear in Stage 1 of Touhou 10: Mountain of Faith. Shizuha Aki is the miniboss, and Minoriko Aki is the boss. They're fought at a rice field somewhere near the base of Youkai Mountain, that Minoriko manages.
Minoriko Aki is of course the more popular one. She's nice enough, but easily frustrated into fighting. She wears homemade yam-scented perfume, which Reimu thinks makes her smell delicious. Of course, Minoriko interprets this as a death threat somehow and attacks.
Fun Fact: While the mob cap is a notorious aspect of Touhou character design, Minoriko Aki is so far the last new character to wear one. She debuted in 2007, so it's been a long time since the "diaper hats" were as ubiquitous as they're assumed to be.
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