I finally tracked this down, and of course the issue was my code.
It took a helpful customer to tell me step by step what they had done.
One button in the app attempted to create a non-essential file.
If the file existed at startup, the contents were used, if not, the app used internal defaults.
Only some of the folk using the app have ever used the button.
And the NEXT time they use the app, it dies because the file was malformed.
On first install, everything works, so it was near impossible to to duplicate, as I could go to any machine and demonstrate it started properly.
Very luckily, this file is created in the Documents folder AND I have exposed that through iTunes, so my workaround is simply to delete the corrupted file.
I’ve uploaded a fixed version to Apple.
Mystery solved.
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