When entering a new volunteer at the organization/opportunity level manually, I entered the email address as given by the volunteer. The email address given was the same as the volunteer's wife, who was already in the system (I was not aware of the email overlap when entering).
Because we have an automated welcome email, a notification that an email would be sent was at the bottom of the Add Volunteer page. When I clicked ADD, the window disappeared and by all accounts I felt safe to assume that I had entered the volunteer into the system and that they had received an email.
When later searching for the volunteer, I could not find a profile, and ascertained (ONLY because their email started with their last name, as you cannot search the volunteer list by email) that the wife had entered the same email, and that Bloomerang did not accept my new volunteer entry whatsoever nor did it send an email.
As soon as I entered an email that was already in the volunteer database, I should have been notified that there was an error and that my manual volunteer entry was not accepted.