Green Glyphosate Treatment with Ferrihydrite and CaO2 via Forming Surface Ternary Complex

Glyphosate (PMG) is a globally used broad-spectrum herbicide and receives environmental concerns because of its moderate persistence and potential carcinogenicity. Traditional PMG treatment methods often suffer from the generation of a more toxic and persistent aminomethylphosphonic acid (AMPA) intermediate. Herein, we develop a green method with ferrihydrite (FH) and CaO2 (FH/CaO2) via regulating the coordination of PMG with FH and Ca2+, where the phosphonate group of PMG preferentially binds to FH and its carboxylate side complexes with Ca2+ released by CaO2, forming a FH-PMG-Ca ternary surface complex. This unique ternary complex can redistribute electrons within the PMG molecule for its C-P activation and C-N bond stabilization, favoring the selective C-P bond attack of superoxide radical produced by the Fenton reaction between CaO2-derived H2O2 and FH, thus generating environment-friendly glycine instead of AMPA. The FH/CaO2 process realizes over 99% PMG degradation in industrial wastewater within 1 h, with residual PMG < 0.1 ppm and AMPA < 40 ppb. More importantly, the CaO2 consumption was as low as 3.1 mg of CaO2/mg of PMG, one-fifth those of previously reported CaO2-based counterparts. This study provides an effective and environment-friendly PMG treatment strategy and highlights the importance of surface coordination modes on the degradation pathway of PMG.