Can we refer to female officers as Madam?

I wouldn't, just stick with "Ma'am". My bet is that saying "Madam" would make a U.S. female officer feel as if she were a fragile English woman serving hot tea or something along those lines and she wouldn't feel respected. This isn't the U.K.

Proceed with that one at your own risk.

I think I'd stick with Mam and not branch out beyond that and if male keep only Sir both of which are polite and respectful. .