Yes no problem with just water for testing, not worth wasting good coolant.
Sorry I did not post thoughts about the cause. A stuck thermostat is probably the most likely cause I think initially, a water pump is possible but I think its the TU units mainly where the impellers can rot or fall off, something I've only seen a few times though.
Rad block, I suppose that's possible but with it having new coolant a while back I would of thought it would of been noticeable by things at the time, thinking back was the coolant that drained when you did the pump then really bad / rusty ?
I think once you've filled it and ran it keeping an eye on it and the top (and bottom) hose / heater / temp gauge you'll be able to determine the cause.
A more rare possibility is a foreign body in one of the water hoses, but I guess as its warming up going around feeling the hoses etc as normal will give a clue to this.
Once it boiled it will eject it due to the pressure as you know, that's pretty normal (but a bit extreme if its that hot)
I'd not worry now until you've filled it and ran it and picked up some more information.

Andy.
91 205D-Turbo, gone but still missed
02 106D, TUD5B, gone but not really missed apart from the MPG