We prove that every lower unitriangular and totally nonnegative matrix gives rise to a family of polynomials with only real zeros. This has consequences for problems in several areas of mathematics. We use it to develop a general theory for chain enumeration in posets and zeros of chain polynomials. The results obtained extend and unify results of the first author, Brenti, Welker and Athanasiadis. In the process we define a notion of h -vector for a large class of posets which generalize the notions of h -vectors associated to simplicial and cubical complexes. A consequence of our methods is a characterization of the convex hull of all characteristic polynomials of hyperplane arrangements of fixed dimension and over a fixed finite field. This may be viewed as a refinement of the Critical Problem of Crapo and Rota. We also use the methods developed to solve an open problem posed by Forgács and Tran on the real-rootedness of polynomials arising from certain bivariate rational functions.