I have had the headers on my 67 convertible ceramic coated (sterling silver) for over eight years with no discoloration, they where coated by Jet-Hot coatings in Arizona.
In my experience if one header tube is a different color than the rest, that cylinder is running cooler. It could be that spark plug wire is damaged or shorting out, check it with an Ohms meter. Also, check the gap on that plug or its ceramic insulator. I had a small crack in one and it was shorting out against the block.