Just some random thots...
If you have the IP address, have you located the machine? Is it more than one? Or just one? Can you do a stake-out some night? Maybe a strategically placed web cam.
Does it happen every night, or just some nights? If you see a pattern, maybe check it against work schedules.
I assume there would be supervisors at night. Can you talk to them and enlist their support in finding the person? This approach is only flawed if it's one of them.
Actually, since the person seems to have usernames and passwords, I would look for a keylogger instead of a sniffer. Maybe rerun virus scans (make sure your software finds keyloggers). Also try the normal set of freeware (SpyBot, AdAware, HiJackThis, CWShredder, etc). Also look for hardware keyloggers. There are tiny ones that plug between the keyboard and the PC (
Keylogger).
You say you have a web filter installed. Why aren't you just blocking the sites that are being visited? Maybe instead of doing black list filtering, do white list filtering where the only sites accessible are ones that are approved and put on the list. This is a lot more oppressive, but that can put peer pressure on your "surfer" that's abusing the privilege if others know what he/she's doing.