It is the way the pixels capture the image and the interpolation used.
In digital, I always recommend shooting in color, RAW images, and later translate to B&W. This gives you total control on the way the B&W images look as you can emphasize a color and use the RGB layers as you would filters on a lens to create the exact effect you want.
In film, I would recommend shooting in B&W and use lens filters to create effect. You would have all the silver halides available to capture your image. Why? Because color film has three separate layers (sensitive to Red, Green, and Blue light). You would actually negate the color effect of some of the layers when using lens filters)