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Pipe entering the monolith tank bottom right (blue collar) is likely to be the cold water inlet to the tank, if you follow this back, this is connected to the main house water feed.
At some point from the water inlet pipe there should be a connection to fill / top-up the radiator loop, valve might be one of those without a handle and operated with a flat head screwdriver (connection might temporarily disconnected and connected via a flexible hose?).
Although it might near the tank, it doesn’t have to be, it can be anywhere convenient where the central heating loop and cold water inlet to the house are in close proximity - it is however normally reasonably easy to access, as radiator systems do need to be emptied/filled/topped-up every so often.
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OrsonCart
Thanks. The only pipe going into he boiler that was cold to touch while the heating is on (and not labelled 'gas') was the one on the far right - so it'd be a valve on that one presumably? There's no valve on it, so it must be somewhere else in the house - would it being near the monolith make sense?