According to Our previous measurements, waterfalls permanently modify air ion spectra. In this paper we performed a correlative study of these results and proposed some pathways which can produce the observed waterfall ions. The small ion composition near waterfalls should be different from that further away due to gaseous OH- core (water shell) clusters. We assumed that the combination of factors (autoionization, fluctuating charge rearrangement, surface protrusions, collisions, Coulomb explosion) serves as the main source of observed intermediate ions, and an extra source for large ions. Evaporation of droplets produces nearly equal numbers of positive and negative intermediate and large ions. Waterfall-produced intermediate ions can attach to the waterfall-produced larger particles, which creates an additional link between the waterfall intermediate and large ions. (C) 2008 Elsevier B.V. All rights reserved.