It can’t be super-im because paltalk only enable audio in one window.
He was probably on another voice program, skype, yahoo, msn, whatever, no trick. Most sound cards allow multiple programs to use them as input.
Just like playing music you select mixer as input for paltalk, the other one must select mic as input. If you select mixer for the other voice program it’s a bit of a problem because the other one will hear himself with a delay. You can select a different input for the other voice program, like your cam mic.