Well... there's no externally accessable chroma/luma access points that I know of. They're combined inside the video chip on an NES.
Which DOESN'T mean that the software works in composite, or that a clone of the NES has to combine the chroma and luma signals inside the chip.
Fun fact: the arcade versions of the NES hardware converted the chroma/luma signals to RGB inside the graphics chip, so it output RGB even though it still worked with chroma/luma internally.
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I agree though, S-video on a NES would be sweet.