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Surface runoff is the most significant source of water in dry cities like Tehran. The surface runoff is polluted by heavy metals, which their risk level is a function of their speciation. Herein, Tehran runoff quality and the speciation of metals and metalloids were investigated. The results of quality showed that oxidation–reduction potential (Eh) and pH ranged from + 186 to + 230 mV and from 7.31 to 10.29, respectively. Cluster analysis indicated that Cr, Si, Mn, Fe, Pb, Se, Th, Ba, Ni, Li, and Sr had similar behaviors and origins, and salinity played an active role in restricting their concentrations. Eh and dissolved oxygen (DO) negatively affected the concentrations of all the studied elements. The speciation model (according to HSC Chemistry program) exhibited that all the studied elements are stable; however, in two cases, they would become unstable (pH < 7, Eh < − 480 mV or Eh > 1100 mV) and (pH > 10, Eh < − 570 mV or Eh > 970 mV). Also, Ba, Cd, Li, Mn, Al, As, Sr, Cr, Si, and Se are present in bioavailable species and As and Cd in the runoff exist in high toxic oxidation states of + 3 and + 2, respectively. The linear regression of Cu, Co, Cd, Zn, and As with Eh provided a good fit, and all of these metals were significant at levels 1 and 5%. Finally, it is recommended to continuously monitor the Eh–pH changes for investigating the potential toxicity of metals and predicting the metal pollution by regression equations in any other stations. [ABSTRACT FROM AUTHOR]