Spectral Induced Polarization (SIP) is a non-invasive geophysical method that provides characterization of electrochemical processes occurring at mineral-fluid interfaces. Despite growing applications in the field of hydrogeophysics, there have been limited mechanistic interpretations of SIP signals in terms of geochemical reactions. The aim of this study is to investigate the potential for SIP to monitor both natural and engineered geochemical processes. These processes are related to the remediation of contamination and landfill operations, focusing on changes in the electrical double layer (EDL) as a result of (1) redox-dependent immobilization of heavy metals, (2) ion exchange, and (3) mineral dissolution in a porous medium. We carried out controlled flow-through column studies where we combined SIP monitoring, geochemical analysis and reactive transport modeling to relate changes in SIP imaginary conductivity to geochemical changes. Three experimental systems were studied. The first experimental system focused on the sorption and reduction of Cr(VI) onto magnetite-coated sand. SIP observed a short increase in imaginary conductivity during Cr(VI) injection, which was then followed by a continuous decrease, corresponding to the availability of reactive sites in time. This provides evidence that SIP could serve as a non-invasive early-warning tool to monitor reactive barrier performance. The second system was designed to explore ion exchange in municipal solid waste and focused on the ammonium desorption and potassium exchange under various salinities. Imaginary conductivity during low salinity was associated with the ammonium dynamics, while higher salinity conditions were linked to the bulk ionic strength, but still enabled detection of the ion exchange front. Thus, these findings provide further support for SIP as a real-time monitored technique for examining landfill processes. The third system investigated proton-promoted dissolution of Fe(II)-bearing minerals in natural sands. SIP provided evidence of a reproducible V-shaped anomaly of imaginary conductivity that correlates with the advancing dissolution front, indicating that SIP is sensitive to geochemical disequilibrium and moving reactive fronts in porous media. The above three systems provide evidence that SIP provides data beyond bulk electrical properties. Therefore, SIP could be combined with reactive transport modeling and geochemical data to serve as a valuable non-invasive monitoring and management tool for contaminated and reactive subsurface systems in real-time.