Large-amplitude (>100 mV) negative electric (self)-potential anomalies are often observed in the vicinity of buried metallic objects and ore bodies or over groundwater plumes associated with organic contaminants. To explain the physical and chemical mechanisms that generate such electrical signals, a controlled laboratory experiment was carried out involving two metallic cylinders buried with vertical and horizontal orientations and centered through and in the capillary fringe within a sandbox. The 2D and 3D self-potential (SP) data were collected at several time steps along with collocated pH and redox potential measurements. Large dipolar SP and redox potential anomalies developed in association with the progressive corrosion of the vertical pipe, although no anomalies were observed in the vicinity of the horizontal pipe. This discrepancy was due to the orientation of the pipes with the vertical pipe subjected to a significantly larger EH gradient. Accounting for the electrical conductivity distribution, the SP data were inverted to recover the source current density vector field using a deterministic least-squares 4D (time-lapse) finite-element modeling approach. These results were then used to retrieve the 3D distribution of the redox potential along the vertical metallic cylinder. The results of the inversion were found to be in excellent agreement with the measured distribution of the redox potential. This experiment indicated that passively recorded electrical signals can be used to nonintrusively monitor corrosion processes. In addition, vertical electrical potential profiles measured through a mature hydrocarbon contaminated site were consistent with the sandbox observations, lending support to the geobattery model over organic contaminant plumes.