Cheers Andrew, I've used new o-rings, and they are sealed perfectly, the old o-rings were knackered. Because of the layout, it's quite hard to see there, as it's right up against the firewall, but it's not the flanges now.
Deffo looks like head gasket now though, as I've had some more symptoms appear this evening - pressurised coolant, and the level in the expansion tank drops massively if you rev the engine.
I guess the head will be coming off in the next few days.
Incidentally, this started after a minor overheating 'happening'...