If the user is going to require some Internet access then you may have to do it via Security Access Permissions or Software Restrictions on the Browsers involved.
Using Software Restriction Policies to Protect Against Unauthorized Software
can't you just block port 80 for that user. pop and smtp use different ports and blocking port 80 should stop internet access but still allow email access.
I've never tried this I have to say, but it seems logical.
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