A few thoughts...
Leaky coolant tank/cap, or maybe one of the the coolant hoses going to it is leaking. As Ben said, it should be visibly leaking if this is the case. I once had a tiny pin-prick leak on the hose going to the top of the expansion tank that was only visible at high engine speeds (due to the higher pressure).
Over heating coolant would eventually force the cap to vent. What are your oil/water temps like?
Check the pipes going into the bulkhead to the heater matrix, maybe they are leaking and spraying the expansion tank as its quite nearby.
As already said, headgasket could be pressurising the coolant. Ideally you need either a compression or sniff test to confirm.