Well, no surprise here, but I found a few interesting math podcasts. The Math Factor Podcast regularly posts simple math and logic puzzles for entertainment. I also found Travels in a Mathematical World, which makes episodes about math history, current theory, and applied mathematics.
As for library-related podcasts, I found This Week @ Your Library. It is Mitchell Memorial Library's way of keeping patrons informed of current events and happenings at their libraries. It might be an idea that TCCL could look into. In fact, most (or at least many) of the podcasts that are listed under "library" are libraries informing their patrons of their events. While I do think the idea is innovative, I do not really think it is an efficient way of conveying news. Mostly I think the TCCL website is more striaght-forward and practical for such a thing.