When an avatar is updated, the previous one is automatically deleted.
So as far as I know, the only way in which there can be stored but unused blobs is if content is uploaded within the WYSIWYG editor for embedding, and then no longer referenced within the HTML itself.
So this would be a big job of scanning all the HTML in all the posts, as well as collecting all the avatar blob IDs from users (as well as the default setting), and then seeing if there are any blobs in the database which are not referenecd.