We report photoemission experiments revealing the valence electron spectral function of Mn, Fe, Co and Ni atoms on the Ag(100) surface. The series of spectra shows splittings of higher energy features which decrease with the filling of the 3d shell a
nd a highly non-monotonous evolution of spectral weight near the Fermi edge. First principles calculations demonstrate that two manifestations of Hunds exchange $J$ are responsible for this evolution. First, there is a monotonous reduction of the effective exchange splittings with increasing filling of the 3d shell. Second, the amount of charge fluctuations and, thus, the weight of quasiparticle peaks at the Fermi level varies non-monotonously through this 3d series due to a distinct occupancy dependence of effective charging energies $U_{rm eff}$.
