it is possible to check if an email address exists. what you do is simply connect to the remote smtp server for their address and if the server supports it use VRFY and the server will tell you if the username is valid as a mailbox or not, if vrfy is not supported you can try RCPT TO email address and it will give mailbox unavailable if the user doesnt exist. just as a warning some large sites, will say 200 ok for any email address, but a majority of mail servers will tell you if the box is unavailable.
a sample session may be
connect mailserver port 25
helo yourserver
mail from: anything@anything.com
help
if vrfy is contained in return string
then it supports the vrfy command
vrfy user
if 200, box exists
exit
else
no vrfy, use rcpt to:
rcpt to: user@site.com
if return status is 200
mailbox exists, email accepted
else
bad status, box unavailable
quit
additional note, if a box doesnt exist but the mail server says so, it may mean there is a default catchall for the domain, otherwise if a message is sent, it will just return the message.
if you need more info on the mail server stuff or help w/ this program. contact me thru email (drew [at] drew-phillips (dot) com.
or chat line
look in my profile for details
i made something like this a while back for a person, dont hve the code anymore but could certainly help you write a php block for it.