The term pitting is usually used to describe a condition inside the barrel, but it, and probably the marks you describe, is plain old rusting. Rust can be red or black depending on the conditions and the material. Bluing is simply controlled rusting, so the spots could be some discoloration in the bluing. You may be able to remove it with a brass or bronze brush, or with brass wool from the grocery story (sold for cleaning pots). Four 0 steel wool and light oil works OK too, but can scratch if used too harshly.
Jim