How are the users connected to the intranet? Even if they are connected through the internet, they are likely connecting into your system via a VPN (otherwise, we can't really call it an inTRAnet). Therefore, there must be some way to identify inTRA versus inTER-net users. Generally speaking, any IP like this (192.168.*.*) or this (10.*.*.*) is an "internal" address whether it's on a LAN or WAN.
The only other way I can see doing this is to enable Integrated Windows Authentication as well as anonymous access to your web application. If the user is connecting with IE on Windows and they are logged in with an account that is discoverable on the same active directory domain that the web server is on then you may be able to match their identify. However, I think this would regardless of how they are connecting.
I guess the next question really is:
Are you concerned with determining WHO is connecting or HOW they are connecting?
-Peter
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