Apparently the action of DEF relies on thermal decomposition of the the Urea/water at the high operation temperature of the reactor. This sort of reverses the the process that make urea initially which suggests that the low(er) temperature decomposition is very similar merely slower which would explain my the shelf life is longer with lowered temp exposures.
If this is indeed correct than operating with DEF older than the expiration date would probably not have any affect unless it was really old or stored at high(er) temps. Than it probably would just be less effective and take more DEF per cycle.
This is just a guess but Urea is not very complicated so the decomposition byproducts are pretty limited.