Adsorption and oxidative transformation of phenolic acids by Fe(III)-montmorillonite

Phenolic acids participate in various soil processes and are of great concern due to their allelopathic activity. The interactions of phenolic acids (ferulic, p-coumaric, syringic, and vanillic) with montmorillonite enriched with Fe(III) was investigated. Adsorption of the phenolic acids on Fe(III)-montmorillonite was accompanied by their oxidative transformation and formation of Fe(II). Oxidative transformation of phenolic acids was affected by their molecular structure. The order of maximal transformation at the initial acid concentration of 20 mg/L on the surface of Fe(III)-montmorillonite was ferulic (94%), syringic (60%), p-coumaric (35%), and vanillic (25%). Benzoic acid which was used as a reference aromatic compound exhibited only 5% transformation. Removal of the phenolic acids from solution increased with decreasing pH. LC-MS analysis demonstrated the presence of dimers, trimers, and tetramers of ferulic acid on the surface of Fe(III)-montmorillonite. Oxidation and transformation of ferulic acid were more intense on the surface of Fe(III)-montmorillonite as compared to Fe(III) in solution due to stronger complexation on the clay surface. The results of the current study demonstrate the importance of Fe(III)-clay surfaces for the abiotic formation of humic materials and for the transformation of aromatic (phenolic) pollutants.