I found out I have the same problem. Seems my keyboard mutes and unmutes Master correctly. But it doesn't unmute PulseAudio.
Channel and Mute symbol react in Volume Control but with no effect. Standard is ALSA Mixer. Do I have to remove ALSA or OSS?
For "hotkeys" you have to know keyboard type and key code. Maybe then you could edit/create a def file in /usr/share/hotkeys/
I haven't tried out Multimedia Systems Selector (gstreamer-properties). Maybe it helps to specify the output ...
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ALSA lib conf.c:3406:(config_file_open) /usr/share/alsa/pulse-alsa.conf may be old or corrupted: consider to remove or fix it