Thanks for the quick reply, @SquareDanceGuy and @george3!

Only economy was available to add to the award, but at even worse times than a 5 hour layover. I think there might be an earlier flight on Air Europa, but by the time I change terminals, etc., it would be negligible.

I do like the train option. I don't know the train schedule but I am assuming it is frequent enough that it probably could get me into BCN sooner. Thanks!