as mr_F said, *@ip comletely disables ident check for predefined user. Even if site checks ident, it wont care if it does match or not (because you have specified *).
Yes, I'm 100% sure about that as I got some users too who are behind some spooky FW or they just can't ident because their ISP blocks it...
Btw, you could try to delete all IPs for that troubled user and just add * (just for test). I bet $100 that he'll be able to login (yep, even if site will check his ident as you've said and even if that ident doesn't match (but it will match cause we've specified "*" which means ANY ident, even none)).
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