Occurring naturally siderite (FeCO₃) was used as the heterogeneous catalyst to activate peroxodisulfate (PDS) for the degradation of sulfadiazine under different initial pH values. The findings of this system exhibited various ROS (e.g. ¹O₂, SOradical dot₄⁻ and radical dotOH) present during a wide range of pH values. Among them, ¹O₂ could significantly facilitate the initial degradation rate, and the increased pH enhanced the role of ¹O₂. The factors including initial pH values, siderite dosage, PDS concentration, initial contaminants concentration, and water matrix were discussed. The role of each ROS was investigated through quenching test and electron paramagnetic resonance (EPR). Furthermore, the comprehensive degradation process was proposed based on the LC-MS results. And the cycle test demonstrates the reusability of siderite at a pH of 3. Accordingly, this study is of great significance for understanding the degradation of such sulfonamide pollutants in the siderite/PDS system.