To support older browsers you could use something like xpaths.js but safari, chrome, firefox all support document.evaluate() and manipulating the element is a no brainer just do addClass().
https://github.com/andrejpavlovic/xpathjs
Despite being a jQuery fan (I've used it to build 4k line jquery chrome extension) I find it much easier to just look up the javascript equivalent, more than often, it's worth knowing since it frees you from using library.
But keep at it, I think maybe if you could build something that does a very good job of highlighting dom elements on mouseover/mouseout with some intelligent highlighting (simply attaching event handlers to all elements on the dom page produces a jerky) I could see that being quite useful.
All in all, take my view with a grain of salt, just because I failed to see a use case and think it's more cost effective to know the DOM manipulations with javascript directly, does not mean that somebody out there might justify it's use.
Good stuff!