The specificity of the chemical composition of underground waters of the Quaternary aquifer complex of the Azov sea catchment basin, which dominates the flow volume, is considered. Using deterministic models, the volumes of runoff of the main ions, common iron, and methane are calculated. The predominant ones are sulphate, chloride-sulphate or sulphate-chloride, less often bicarbonate and chloride waters, usually of a sodium or calcium cationic composition. The average annual volume of underground water flow in the Quaternary complex is about 0.024 km3/year (66,300 m3/day). The average annual value of underground ion runoff is ~387,000 t/year, with 47.2% of this value being accounted for by sulfate ions. The average annual underground runoff of total iron and methane is ~0.968 t/year and ~0.037 t/year, respectively. The dominant contribution (over 98%) to the volume of underground runoff of the main ions, common iron and methane is made by their runoff from the Northern sections of the sea catchment basin, which is mainly due to the distribution of the module of underground water flow.