The first mistake that all seem to make is to think ALL Fire Departments are the same. Departments with no diving in the area may have lessor quality than a department on Cape Cod, but the "MAY" is very important. It will all depend on the quality of the departments maintenance and control. I have been in some departments that have systems way better than any dive shop and have also seen systems that got condemned and now have to get their bottles filled at a dive shop. I have also seen some dive shops that have crap for air quality.
But in general, a Fire Department that supports a dive team will have good air and most likely be better than a dive shop as they are subject to much higher Inspection standards than any dive shop will have (OSHA, insurance, etc.) and have customers, the dive team, that usually know all about what they need and want. I will also go out on the limb and say that a Fire Department near diving in an area with low dive shop coverage will have some divers on the department and better air - Cape Cod, Maine, Northern New York come to mind. I have also seen some of these shops with a few bottles of O2 and He for some reason.
So, no 2 fire departments are the same, you need to ask, and they may not fill your tank anyway unless they know you.