In-depth Analysis of the Roles and Mechanisms of Sulfate Radical and Hydroxyl Radical in the Degradation of Metal-Cyanide Complexes

Abstract

Persulfate-based advanced oxidation processes (PS-based AOPs), characterized by the coexistence of SO₄•⁻ and HO•, have been proven effective in treating a series of cyanide-bearing pollutants. However, the mechanisms of these reactive species in the degradation of cyanides, especially metal-cyanide complexes, remain unclear or contradictory. The degradation behavior of representative cyanides (including potassium cyanide and potassium ferricyanide) at different pH conditions (2, 7 and 12) in thermally activated persulfate system (T = 60°C) was explored, and the roles of SO₄•⁻ and HO• in cyanide degradation were explored by leveraging the distinct characteristics of reactive species under different pH conditions. The study found that both HO• and SO₄•⁻ can react with free cyanide (CN⁻ and HCN). However, the reaction barrier between CN⁻ and HO• is lower than that between HCN and SO₄•⁻, resulting in a higher removal rate of free cyanide under alkaline conditions compared to acidic and neutral conditions. For complexed cyanide, the complex bonds in ferricyanide were completely broken within 24 hours by thermally activated persulfate at pH 2, releasing free cyanide, indicating the effectiveness of SO₄•⁻ in breaking the Fe-C bonds in ferricyanide. In contrast, ferricyanide was barely decomposed at pH 12, implying the inefficacy of HO• in breaking the Fe-C bonds. This study also innovatively found that SO₄•⁻ breaks the Fe-C bonds by oxidizing Fe(Ⅲ) in ferricyanide to Fe(Ⅳ) or Fe(Ⅴ), releasing CN⁻, which is then converted to CNO⁻ by SO₄•⁻ and HO•. CNO⁻ is further mineralized to NO₃⁻, NH₄⁺, and N₂ through hydrolysis or oxidation reactions. This research clarifies, for the first time, the activity of SO₄•⁻ and HO• toward cyanide degradation in PS-based AOPs.