With the header tank cap off check for a steady stream of water from small hose when revved. Mine was blocked at the radiator end and this caused pressure in the system to an extent that I lost water and when removing the cap even when the car was cold the level tended to want to overflow.
I have to admit I had heat issues once, the water return pipe to the expansion tank was blocked, but you should be able to see a steady flow of water from that pipe into the tank!
Yeah could be a worn ring on no. four, head off time I'm afraid mate! Emulsified oil on the tip a sure sign of water ingress on a bore! Sorry fella it might be just one new ring, new gasket, flush, light skim on the bore and light skim on the head?
No.1's where your problem has occurred, I'd say. The dark-coloured exhaust valves are the odd-ones-out.Excuse me borrowing/doctoring your pic, but I think the fire-ring has leaked where the yellow arrow is pointing:When getting the head skimmed, ensure that enough material is taken off to 'make-good' any erosion of the alloy between the waterway nearest that point, and the area which that fire-ring of the gasket occupies.