Comparing the abiotic removal of glyphosate by β-MnO2 and δ-MnO2 colloids: Insights into kinetics and mechanisms

Glyphosate as an effective broad-spectrum herbicide is frequently detected in various water and soil resources. Given the ubiquity of β-MnO 2 and δ-MnO 2 colloids in groundwater and soil, the abiotic removal of glyphosate by MnO 2 colloids was investigated. β-MnO 2 colloids exhibited superior glyphosate removal efficiency, up to 37%, compared to 21% for δ-MnO 2 colloids at a pH of 4.0. Glyphosate removal involved simultaneous adsorption and oxidation process , identified by HRTEM , NH 3 -TPD, XPS , LC-MS, FTIR analyses and the occurrence of aminomethylphosphonic acid (AMPA) and Mn 2+ . Moreover, adsorption dominated the removal of glyphosate by two MnO 2 colloids. The solution pH had a substantial effect on glyphosate removal. Co-existing ions in the solution, such as carbonate (CO 3 2− ), phosphate (Na 2 HPO 4 , NaH 2 PO 4 ) and humic acid (HA), were also found to impede glyphosate removal. Phosphate, in particular, exhibited a strong competitive effect for adsorption sites on both MnO 2 colloids. Of them, the removal of glyphosate by β-MnO 2 colloids was more prone to occur due to its higher specific surface area , abundant oxygen vacancies , and moderate acid sites. However, δ-MnO 2 colloids presented a stronger oxidation capacity than that of β-MnO 2 colloids due to the quicker generation rate of Mn 2+ . Finally, AMPA was the same products by two MnO 2 colloids in the oxidation process, revealing the degradation pathway based on the cleavage of C–N bond. Therefore, by comparing kinetics and mechanisms of glyphosate removal by β- and δ-MnO 2 colloids, this study improves us better understanding for the behavior of glyphosate in the environment.