Fools rush in . . . that would be me!
I believe the dark grey, almost black, finish of the front and rear surfaces and the insides of the charging holes of the S&W Titanium cylinders is some type of anodizing.
We have three revolvers with Titanium cylinders, all of which have been fired several hundred rounds with both commercial and hand loaded ammunition.
All three have some discoloration on the inner surfaces of the charge holes. One has a single, small, irregular dark spot in only one charge hole. One has lighter brownish "stains" primarily on the surfaces closest to the center of the cylinder of all the charge holes. The third has dark brown stains that appear to be located in the areas of all five charge holes that get the most smokey residue when firing light 38 special loads.
All of the surfaces, stained or not, are glossy smooth and none have been cleaned with harsh chemicals, although I do occasionally use a bronze brush.
I have read several gun articles commenting that the "coating" S&W applies to these surfaces is a form of anodizing.
I know that, commercially, most anodizing, especially of aluminum, is applied to create a surface that can be dyed to various colors.
So, it makes sense to my simple mind that the dark spots and lighter stains are all staining of the relatively porous layer of anodized Titanium and no cause for alarm.
In any event, since all of mine were purchased new and all exhibit these stains to a greater or lesser degree, but still function perfectly after hundreds of rounds fired, I am not going to worry about it.
Remember, Your Mileage May Vary and that I am NOT a gunsmith.