It's Celsius. I'm not a licensed electrician so
@FlasherZ can probably correct me if I say anything wrong. But the temperature rating is for the insulation and assembly of the entire cable and conduit. NM cable is non-metallic and should not be in any conduit, so must always use the 60° column, regardless of other factors. The 90° column can be used if the type of wire (THHN is what we're discussing here), the conduit, how many other wires are in the "raceway" (I think it's called the fill factor, and is actually taken as a derating of the full ampacity), and the ratings on the terminals are all at 90°. So if he really put 4AWG THHN in appropriately sized conduit between the panel and wall connector, yes you can use the 90° column and get 95A (not 100A). Set your wall connector at 90A (I don't think it has a 95A setting). The 100A breaker is then okay, cause if the ampacity doesn't match a standard breaker size, you can go up one (probably subject to some caveat I'm not aware of). Or you could go down to a 90A to match the wall connector setting and not worry about it (but possibly not a cheap and easy to find breaker).