Opencast lignite mines, pit-head thermal power plants, and other associated industries in the Neyveli mining and industrial complex generate huge quantities of solid and liquid wastes that are contaminated with heavy metals. Some of these are toxic or carcinogenic at sufficient concentrations. Copper, Zn, Mn, Fe, Ni, Cd, Cr, Co, Pb, and Hg concentrations in surface water in the study area are from 2 to 1200 times higher than average concentrations in river water worldwide. Heavy metal contamination in the natural reservoirs (Peria, Kolakudi, Walaza, and Perumal Ponds, and the Paravannar River) is mainly due to the discharge of untreated mine water, fly-ash pond water, and effluents from associated industries. These waters have long been used for bathing, washing, animal watering, etc. Untreated mine and industrial waste water, and natural reservoir water have been used by nearby villagers for irrigation for the last four decades, which may have led to deterioration of soils, surface water, and groundwater. Heavy metal analyses of mine water, fly-ash pond and industrial effluents and the natural reservoirs reveals that Co, Cr, and Hg are above the recommended irrigation water quality standards in 17%, 75%, and 100% of the samples, respectively. Most samples were within the permissible limits for Mn, Ni, and Fe, while Pb, Zn, Cd, and Cu were within the limits in all samples. At elevated concentrations, toxic metals like Cr, Co, and Hg can accumulate in soils and enter the food chain, leading to serious health hazards and threatening the long-term sustainability of the local ecosystem.