As @Gasguru suggest, once the HW cylinder is isolated then it should only run until the pressure is released within the cylinder, if it doesn't stop within a minute or 2 then the cylinder isn't being isolated from the mains properly and still supplying the cylinder, that'll be why you can't replenish the air bubble and why the relief valve is still passing.
First job you need to do is figure out how to isolate the feed to the cylinder and why the mains stop tap isn't isolating everything in your house.
I'm just posting an update in case it helps people in the future.
The water continued to drip through the tundish even if the water was isolated. This was because the pressure in the cylinder was pushing the cold water back up the inlet pipe at the bottom of the cylinder.
The pressure relief valve had indeed failed. A crack was clearly visible on the seat of the valve.
I sourced the new valve, the plumber fitted it and the tundish is now dry!
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