Well - my experience of POP3 servers says that this solution won't work either.
As you can imagine, for security reasons, if you connect to a POP3 server and try a username/password combination it will (generally) always return you the same error whether the username exists or you just got the password wrong. Whether this can be modified by the system admin of the server I don't know. But, on the whole this does not happen so you will still have no idea whether that account exists.
Additionally, what about catch all boxes which then get distributed internally using an Exchange server (or something else with the same capabilities). The POP server will only have the catch all box and all the mail will come in through this route. The Exchange server is then responsible for distributing to the actual real accounts internally and bouncing back as required.
So - as I said before, there is no real way to perform this action without having some sort of user response to verify that the email address does actually exist.
To this end - I agree with planetsim. If you want to ensure that the mail address exists on account activation (or whatever), then you need an activation system where the user has to validate their account before continuing (i.e. before their account gets activated). This system is in use in lots of large systems (in fact most things I tend to sign up to these days uses something like this).
So - hope this helps 🙂