Breakthrough curves (BTCs) are a valuable tool for qualitative and quantitative examination of transport patterns in porous media. Although breakthrough (BT) experiments are simple, they often require extensive sampling and multi-component chemical analysis. In this work, we examine spectral induced polarization (SIP) signals measured along a soil column during BT experiments in homogeneous and heterogeneous soil profiles. Soil profiles were equilibrated with an NaCl background solution, and then a constant flow of either CaCl2 or ZnCl2 solution was applied. The SIP signature was recorded, and complementary ion analysis was performed on the collected outflow samples. Our results confirm that changes to the pore-water composition, ion exchange processes and profile heterogeneity are detectable by SIP: the real part of the SIP-based BTCs clearly indicated the BT of the non-reactive ions as well as the retarded BT of cations. The imaginary part of the SIP-based curves changed in response to the alteration of ion mobility around the electrical double layer (EDL) and indicated the initiation and the termination of the cation exchange reaction. Finally, both the real and imaginary components of the complex conductivity changed in response to the presence of a coarser textured layer in the heterogeneous profile.