Magnetic properties of impurities at ferromagnetic surfaces and interfaces have been investigated performing Perturbed Angular Correlation (PAC) measurements in the ultra-high vacuum chamber ASPIC (Apparatus for Surface Physics and Interfaces at CERN) using different PAC probes. We present the measurements of magnetic hyperfine fields (B hf) at 111Cd probe atoms (i) in Pd covered by Ni, (ii) on Pd-decorated Ni surfaces, (iii) and on pure Ni surfaces at a variety of local structures like terraces, steps, kinks. The results yield a deep insight into the interplay of structural surface roughness and magnetic roughness on the atomic scale. Correlating the experimental B hf values with the number of their nearest Ni and Pd neighbours, the coordination number, nonlinear dependences were found. These findings are compared with recent theoretical studies which were prompted by the experiments.