One of our techs reported that when trying to go to the home page of a specific website in IE 7-8, they were instead being routed to a slightly different URL. She did some minor troubleshooting by trying the same site from another workstation with no problems. We also tried the same URL and were not able to recreate the problem. We took a few different approaches and after an hour we gave up.
Still curious, I connected after hours to the workstation exhibiting the problem. I started by logging on as a local admin account, which would ensure that domain account policies would not interfere and could be eliminated as a cause, and I was able to reproduce the problem. This was telling because it meant that we were likely dealing with an issue that was workstation specific, not user, otherwise when the tech logged into the other workstation when she tested earlier, her roaming profile would have included the user specific settings, i.e. the suspect setting was not residing in HKCU but instead likely present in HKLM. Earlier tests also further isolated the issue specifically to IE since other browsers were not being redirected.
The breakthrough came when I decided to stop ignoring the site content. The site in question was wageworks.com. Here is the site you should be directed to when you type this into your browser: