Thermal compound isn't the problem. Even a poorly mounted water block that DOES have some kind of TIM between the CPU heat spreader and block isn't going to run at 80°C at idle unless it was VERY loose.
Old paste might account for MAYBE a 5-10 degree difference, if it's VERY old, but not like what they have.
If this is an old cooler, then it's very likely you either have lost some amount of coolant and have a serious air bubble inside OR more likely, the pump shaft has worn itself free of the impeller and so the pump motor is turning but is not actually pumping anything. I would highly advise that you not run the system like this. At all. 80°C should be a max temperature, not an idle. Anything above that is trouble.
Replace the pump would be my advice, if this is an old cooler. If it is a fairly new cooler, try lifting the front of the case up by about ten inches, then lower it. Then lift the back up, then each side. Sort of elevate one end and then roll it around to see if there is an air bubble that can work itself free. This happens OFTEN with AIO coolers.