While that is a top quality PSU, until Man can create perfection 100% of the time, there will always be units that come off the line defective or that fail pre-maturely. I would swap in a known good PSU and see (smell) what happens. You might even be able to jam your nose into the back of the PSU and determine if the smell is coming from there. Or remove the 4 PSU mounting screws and carefully swing the PSU out of the PC case to help further isolate the PSU and any smells it might be generating.
I also agree with E-Tech that dust - especially if it contains lint and organic matter (hair, dander, insect, etc), can smell when hot. However, electronics, when overheating/burning does indeed have a very distinct smell that does NOT smell like burning lint, dander, hair or insects. So that is concerning if you are certain it is overheating electronics creating the smell. Because there are deadly voltages within the PSU, eliminating that from the equation should be your top priority.
I also recommend cleaning the PSU - I use an air compressor equipped with an appropriate
inline moisture and particulate filter -
essential when cleaning electronics (or air-brush painting birthday cakes or faces). Never see how fast you can make a fan spin - you can easily exceed design limits and destroy the bearings so I use wooden glue/Popsicle sticks to hold the blades stationary when blasting.
Finally note that one of the problems with water cooling is other heat sensitive devices can be neglected. These include the VRMs surrounding the CPU socket and the chipset. A decent
laser targeting infrared thermometer is extremely helpful when trying to pinpoint the source of heat.
What is the 100c and 102c temperature readings?
Most likely "ghost" readings from non-existent sensors. Some times HW monitoring programs don't know what to do when they try to display a value for a sensor that does not exist, or is not working properly. I think your temps are good, but I would verify with another program. You might try
Speccy (from the makers of CCleaner) and see what it says. Or my favorite,
HWiNFO64 is also very (if not too) informative. When using it for the first time, I recommend you select “Sensors only” when prompted. Then scroll down to your motherboard’s section to see the temps. While there, make sure your +3.3V, +5V, and +12V voltages are all well within the allowed ±5% tolerance deviation.