I work at Mailgun and this may explain why when our customers use Facebook as a customer acquisition tool they inevitably end up with a large amount of bad email addresses, leading to a poor email sending reputation or worse.
While I'm not familiar with the information Facebook shares through Facebook Connect, this seems to be a big short coming. You may not be getting the customer's real, current email addresses.
We have to tell people that Facebook is not a reliable way to obtain valid email addresses. The only way to properly do this is to have customers submit their email addresses directly to your own signup form and then validate them with a confirmation link sent to that address (double opt-in).