Nope, both front: and hw: are bit-perfect ALSA outputs that bypass (don't go through) any system mixer. If you use the Pulse output, everything is resampled and dithered to 24-bit/48 kHz by the system mixer if I recall correctly.
ALSA is the way to go. If you have both front: and hw: as choices (like I do on Ubuntu), I tend to choose the hw: output for no any specific reason. However on my Arch Linux install I only have front: as an output option so I use that instead. There's no difference in quality and choosing between them is a personal choice. EDIT: I now have the hw: outputs on Arch Linux - thankfully it was easy to do by simply porting alsa.conf and alsa-base.conf from Ubuntu to Arch Linux and the hw: outputs work great along with everything else sound related.