Cheers all. The culprit was identified shortly after I posted the above but I forgot to tell you 🙁
Downstairs neighbour came in saying there was water coming down the wall…turns out a thermo rad valve was leaking. I just turned them all off and drained the rest (the rad in question is currently disconnected), seems OK.
Off to B&Q for a new valve then…
While we’re at it I need to re-install a rad into the system, would I get away with re-connecting the pipes (9mm) without draining the system entirely?
Once I’m done can I simply allow water badk into the rad system and bleed radiators, or do I need to do anything with the boiler given it’s at the highest point and there’s bound to be air in there?