Passivation of anode is a main challenge in the electrochemical synthesis of ferrate(VI)((FeO42-)-O-VI, Fe(VI)). A series of electrochemical approaches were employed including polarization curve, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS) to analyze the physicochemical processes involved in electrochemical synthesis of Fe(VI) using sponge iron and cast iron anodes. The results demonstrate that the sponge iron anode achieved higher yield of Fe(VI) compared to grey cast iron anode. The optimum condition to generate Fe(VI) using sponge iron was 35-50 degrees C and 30 mA/cm(2). Significantly, the sponge iron anode could generate Fe(VI) for a long duration (>10h) under these conditions; possibly suitable for large scale synthesis of Fe(VI). The prepared Fe(VI) solution was used to treat antibiotic (sulfamethoxazole (SMX)) and pesticide (atrazine (ATZ)) in water. At a molar ratio of Fe(VI) to SMX as 20:1 in the pH range from 5.0 to 9.0, almost complete oxidative transformation of SMX could be obtained. Comparatively, oxidative transformation of ATZ was incomplete (similar to 70%) even when [Fe(VI)]:[ATZ] = 87 at pH 5.0-9.0. Fluorescence spectra and cytotoxicity studies suggest that the oxidative transformation products of both SMX and ATZ possess lower toxicity than the parent antibiotic and pesticide, respectively.