Because of her being spayed, the smell is enough to set off marking. I noticed the same thing here whenever a female got spayed, the male dogs go on a marking spree. As soon the hormones get back to normal, they would stop. As to him attaching her, that is not normal. Are you sure they are not just playing? When mine get to playing they sound like they are tearing each other apart, but if you stop them, there is no blood or even slobber on any of them, they are just very vocal about their playing.