Onvn
The short answer is no. Just because a DAC is 24/192 capable does not mean it modifies the incomming data in any way. You need to look for a DAC that has a sample rate converter (SRC or ASRC), then, yes it will upsample the incomming data. I don't know for sure if the Spitefire has a SRC/ASRC, but I don't think so.
The other posters comments on only buying 24 bit DACs also doesn't make much sense, unless you are actually usuing your computer to alter the bit depth of the data on the fly (or you have a Meridian 518 or similar). Playing CD based music, without having a plug-in to convert it to a 24bit data stream, will have no benefit on a 24bit DAC unless it reprocess the data, and these level of DACs just don't do that.
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