The most probable solution is that they do email piping.
They insert the ad with an identifier like "job-fepsd-1120347193" alongside the real email.
Then they receive the email by piping it to a php script (check google for PHP and Piping for good resources on the subject).
The script then search for the unique identifier and associate it to a real email. It forward the email received to the real guy after.
There is also another possible solution (but less possible), they might be using POP3. The would then just cron a check each X minutes on a catch all adress and then forward the message to the right guy.