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Something like 24/96 audio literally contains more information than a 16/44.1 CD-quality file, but my understanding is that 16/44.1 is indistinguishable from anything higher by human ears. I've never done one of those blind ABX tests or anything but if 44.1 kHz audio can accurately encode sound up to 22 kHz per the Nyquist sampling theorem, that's already just above most people's threshold of hearing anyway, so why even bother with 24/96 unless you're an archivist?
The point is that with HiRes recordings, you often get another mix of the original tracks. With CD quality you mostly get a mix which sounds good on budget equipment. With HiRes recording you often get a mix which unfolds its qualities on high quality equipment.

I tested it - no double test and not blind, difficult enough to get same volume - and I found more "music" in those HiRes mixes, the sound left the speakers in a better way, detached of the source.
 
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