Variations in magnetic or electrostatic confinement fields give rise to trapping separatrices, and neoclassical transport theory analyzes effects from collision-induced separatrix crossings. Experiments on pure electron plasmas now quantitatively characterize a broad range of transport and wave damping effects due to "chaotic" separatrix crossings, which occur due to equilibrium plasma rotation across θ-ruffled separatrices, and due to wave-induced separatrix fluctuations.