Well, let's take a look at Barney: he teleported to Xen to set the coordinates for scientists to escape from Black Mesa - and he didn't even wear a helmet or gasmask (like Shephard), or something like that. And he haven't suffocated from the air in Xen! So, I guess, it is able to breath in there.
Plus theory: I think the scientists from Black Mesa actually forgot to identicate the atmosphere in Xen. So, that reveals the reason, why all these scientists, that were in Xen (I actually mean these dead bodies in H.E.V. suits) are wearing H.E.V. suits.