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Mine tailing ponds are environmental hazards because of high susceptibility to leaching and erosion by water and wind. Vegetation establishment is an effective technique to reclaim tailing ponds but requires knowledge of the spatial relationship between the structural composition and physical and chemical properties of soils. In this study we have demonstrated the use of electrical resistivity imaging (ERI), combined with soil chemical analyses, to determine the structural and chemical composition of mine tailing ponds to assess efficient measures of environmental protection. We used a Syscal R1 resistivity meter to generate two- and three-dimensional (2-D/3-D) ERI images from El Lirio and Brunita mine tailing ponds. Soil samples were collected at 1-m intervals to a depth of 15 m, and were analyzed for pH, electrical conductivity and cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) contents. Results show that materials in the ponds can be classified into three categories: fine tailings – low ER (<8 Ω-m), coarse waste rock – intermediate ER (8–150 Ω-m), and bedrock – high ER (>150 Ω-m). Our interpretation of the 2-D/3-D ERI images with respect to the historical depositions of materials in the ponds show that at El Lirio, decant water outlet was initially at the center and advanced to the east of the tailing pond as the mining activities progressed. At Brunita, the intermediate ER values on the west side of the pond marked the deposition of coarse waste rock materials released during a pond breakage in 1972. The ERI helped us image the spatial distribution of tailings and its qualitative spatial correlation with chemical properties (i.e., pH, EC, metals content). Low ER values are related to high amounts of Zn, Pb, Cu and Cd. These qualitative relationships underlie the usefulness of the combined geophysical and soil chemical approaches to improve our understanding of the properties of mine tailing ponds in the Sierra Minera (and other parts of the world).