Did something change recently? It used to work fine previously.
The daemon doesn’t do anything fancy, it just requires the correct mixer-name, card and index. If it gets the right values, it should work 
I don’t have the DAC, but can you check if the Volumio API gives us the correct parameters?
You could check by examining the configuration file for vollibrespot
# VLS config
cat data/plugins/music_services/volspotconnect2/volspotify.toml
Also confirm that this matches what Volumio should use
cat /data/configuration/audio_interface/alsa_controller/config.json
Then you could open alsamixer
and check which of the mixers move when you change the volume from Volumio webUI for web radio, and which one changes when you use Spotify connect.
I’d reckon that they will be different mixers…