I wouldn't allow detecting who is concentrating on a spell the PCs in this case. I don't envision concentration as a child concentrating on something, with the tongue sticking out... It's in my mind a low level concentration by the caster, since he is able, without any threat to his concentraiton, to cast a spell that doesn't require concentration, make an attack by fighting in melee (which by itself requires to able to pay close attention to your opponent...) or do any activity except casting another concentration spell, dying or losing a check made when you're hit.
The optional rule where the GM may ask a DC concentration check for other reasons uses the example of "a wave crashing over you while you're on a storm-tossed ship". It's not being bothered by the ship pitching and rolling in a storm, but a wave crashing on you. An immediate death threat of being thrown overboard in the moddle of the ocean => a low DC 10 Con check. So in my opinion, maintaining concentration is a very low intensity task, impossible for (insert magic theory reason) to maintain on two spells but not something that requires any effort otherwise. I can totally see your NPC being able to chit-chat at a social event without giving any clue.
Maybe detecting that something is bothering the NPC while speaking with him as you suggest, but not pinpointing "she's maintaining a spell effect".