Since the user had a device prior to this, they can probably receive external email. However, you could test that by removing them from the BES and then kicking off the activation on the device. This will send a request to RIM and a message will be sent to the user's email address - and get stuck in their desktop inbox (if the user was on the BES, this message would be processed quickly and you would probably miss it). If that works, then the issue is something else.
Oh, another thing to try is to try activate the device for someone else and see if that works. I have a couple of people who have agreed to let me 'use' them when I'm having activation problems. If I can activate it for one of them, but not the person who needs the device, it narrows down issue to that user's email account.
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No longer a BES Admin, but it was fun while it lasted!
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