As long as the CPU block is on properly, the most likely thing that could cause those temps is an airlock or failed pump in the AIO.
Double check the pump to MB header connection to ensure it's still connected. If you've reset the BIOS recently, ensure the header is still in WaterPump/Continuous mode. The BIOS sensor page should show you the pump speed.
With the pump in the orientation you have now, its possible you have an air bubble stuck in the block. To remove it, take out the rad, invert the case and hold the rad above the cpu block while the system is running so that any bubbles rise into the rad. If it has a top up port, top it up first.
With all the strange behaviour I think it's looking likely it's a motherboard issue.