Just received my Mac Pro 2013 and slotted in 2 pieces of Crucial 16GB x 2 RAM (1866). That will theoretically bring it up to 40GB (with the 2 x 4GB stock) but everytime I powered up, there was a loud beep every few seconds and it is definitely a RAM issue.
Took out the stock ram and left the 2 x 16GB alone and the machine flew.
So, it may be safe to say for now (given the lack of info on this) that mixed capacities do not work in the new Mac Pro.