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No problem. I thought that misdirection was actually the cleverest part of the puzzle, and sent me down a rabbit hole for as long as it took me to solve the rest

Hi Brendan, it's taken a while but I think the penny has dropped. I've always pronounced the silent letter.
Cracking puzzle but I think 22d is a bit 'overworked'!

Quisling, on reflection you are probably right as 'in Alabama' could be removed although it establishes 'in America' so fair play. I'd actually considered the correct themed part early on but my lifelong habit of pronouncing the silent letter (which Chambers has as 'humerous' as per Flanders and Swann) kept me up the gum tree (:o) Mea culpa!!

Lumen, 22 is a thematic clue (as you've probably realised). The first syllable is your buffalo with a silent G, the second the soldier (GI ***). They're then swapped to give the name of Jupiter's wife. You might find it easier to work backwards with this one.

25: It's an anagram of SNOWIER following a two-letter word for THROUGH from which the second letter, Y, is extra.

Can you give me a final nudge then? Seems to be enough going on in 22d to fill eight or nine cells, not four!

Thanks Loge, posts crossed.
AND...it’s not in Chambers, albeit mentioned in preamble.
I’ll work on 35 now.

One resembling Buffalo + GNU
Alabama soldier = JOE
GNU-JOE when treated thematically gives the entry

22 was my last in because Chambers doesn't give the thematic meaning of it. It isn't too hard to find online, though.

25a had me puzzled for a while, even with the answer, but a google of 'The ********' resolved matters. I wasn't aware of the origin of the term.

Sorry, I meant 35a.