Whether or not an app work with straight WiFi is up to the app developer. The BB OS provides multiple network APIs. As for RIM developed apps, they will always use the cell network for Internet access. Other apps such as Opera Mini offer the option and default to raw sockets for Internet access and thus can function off only the WiFi link. Google based apps (mail, sync, maps, voice), all the RIM developed Instant Messaging, and Facebook, are all cell network only apps. You can facebook via the mobile website in Opera though (m.facebook.com).
You can use Opera Mini for web browsing and LogicMail for mail access if all you have is WiFi, however you will need to download those apps on your computer and push them to the phone via the desktop manager. The Pandora radio app ca go via WiFi or cell.
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