It actually makes the biggest of differences!
No headphone driver can really go below 40ish hz (most state 20hz-20khz but do your research and you'll realize its more then 10db below at those frequencies), to do that you need a >7" driver. I've Paradigm 9se MK3's with 2 8" glass-composite drivers and a huge port at the bottom tuned to 32hz; i can benefit from this card, but still not to the fullest
The real treat here is the SNR. My power amp has 122db snr and is class a... so i definitely can make use of the Asus

Most receivers / amps are a good bit below 100db though, so for mainstream people there's little use in this
And as for the sampling rate, anything less then 192khz and you can hear the difference with a good setup ($3000msrp++).
Regarding the 90khz ceiling... there's also use in that! Although most humans can't hear even 20khz, the are some supertweeters that produce more then 100khz; although we can't hear them, constructive and destructive interference from those waves alters other waves around you, and some things resonate at those frequencies thus altering their sonic behaviour

That tiny bit of difference (perhaps even smaller then the gain from using premium cables, [if going even smaller is possible:P]) is sought after by enthusiasts and crazies with boatloads of cash alike!
Props to asus. Of course many audiophile cards (no, not x-fi, the real stereo and recording cards) have already beat them to the punch (albeit in a different pricerange entirely)...
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