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Hmm .... if you add words to the default wordlist, then its file should be updated/written to at every time. There is no other way to "remember" it between Sigil sessions.
You might try exiting out of Sigil instead of leaving Sigil open just to see if that forces the write. Or alternatively if you have the target folder already open on your OS Desktop watching, you may want to close that folder and then reopen it to see if the window itself was just not updated.
Please let us know what you find.
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