That's Prime95 version 29.4,which will use AVX instructions on Haswell or newer cpus. What this means for you is that the cpu is realistically working at 120% in temps comparisons. This is a known thing for Haswell and newer. However games don't use AVX, neither does 95% of consumer applications, it's mainly used by professionals and a few testing apps like Cinebench and Asus RealBench.
For a more accurate assessment of what a pc will go through at a standard 100% load, delete the Prime95 version 29.4 and use Prime95 version 26.6 small fft instead, as it does not use AVX.
As far as exhausts go, you have an Aio. This takes just the cpu heat and exhausts it out. The case exhaust is just for the rest of the pc including the gpu. Some of the case heat will also be absorbed by the radiator as its an exhaust too. With a normal air cooler, the cpu dumps its heat into the case, so case exhausts will be hot. With the Aio, that part is skipped by direct exhaust instead.
No, your pump isn't failing, you just haven't adjusted to the differences between AIO's and aircoolers yet.