Freebase pretty much covered it all. The closest thing you'll get to a 'sign' without approaching is eye contact, and that is no guarantee. They could just have a staring problem.
Approach them and strike up a conversation. If they seem warm and receptive, take it from there. If it seems like they're trying to get out of the conversation as fast as possible, you have your answer. Keep it simple, at the end of the convo ask if they want to get some coffee. It's a pretty safe bet without being too forthcoming.
I guess some signs during conversation would be laughing at your jokes, playing with her hair, body contact, whether she's facing towards or away from you, etc.
Just don't be a shoulder to cry on.
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