I don't think we'd be using volunteers to compensate for systemic issues: the systemic issue here is that we haven't documented all of the spec-quality expectations or given anyone the responsibility for checking those expectations, not that teams are generally too rushed to meet a bar they know about. I think part of rolling this out will be fleshing out the documentation like in the above CL, and I'll need to make that documentation clear that it's the API owners who will have any difficult conversations that are necessary because a spec mentor discovered that a specification wasn't good enough.
On the "volunteer" aspect, all of our active spec mentors work on the web platform full time, so work to help other teams ship their features is within our job descriptions, just like keeping the Chromium tree green is part of our core responsibilities. What I'm trying to ask in this thread is how we can make sure that everyone is actually recognized for this work. I gave some guesses in my initial post, but I want to make sure that everyone's comfortable those guesses will actually work.