Because heat rises, the top card in a Crossfire configuration always runs hotter than the bottom one.
Also, if you don't have a spare slot between the two cards and the cooler is an open design (normal fan instead of a blower than blows outside the case) the top card's fans get blocked by the bottom card.
Oh, and if these are not "load" temperatures Radeon GPUs actually deactivate the "slave" card when you're not playing 3D games and it puts that card in a low-power mode which won't generate heat.