Analysis of adsorption processes of dissolved organic matter (DOM) on ferrihydrite using surrogate organic compounds

Ferrihydrite (Fh) has been recently used in water treatment for removing dissolved organic matter (DOM), but its governing interactions with low-molecular weight DOM are largely unknown. This study aimed to elucidate the influence of chemical structure of DOM on the interactions between functional groups of DOM and Fh using various surrogates representing DOM in natural waters. We tested four surrogate compounds: L-glutamic acid, resorcinol, L-serine, and tannic acid, which represent the main chemical groups of carboxylic and hydroxyl groups; and the Suwannee River NOM (SRNOM) that represents the composition of DOM in natural aquatic systems. Batch adsorption experiments revealed that the DOM adsorption onto Fh was significantly influenced by the steric arrangements of -COOH and -OH functional groups. Both L-serine with α-carboxyl group and resorcinol with hydroxyl groups in meta-position were marginally removed by Fh, indicating that the adsorption of DOM on Fh was determined by their chemical structures and the relative positions of carboxylate and hydroxyl groups. The adsorption of L-glutamic acid was controlled by the pH-dependent ligand exchange of γ-carboxyl groups, which was similar to the SRNOM adsorption. In contrast, adsorption of tannic acid was not affected by pH, which can be explained by a two-step adsorption, namely, ligand exchange followed by multi-layer adsorption to the partitioning phase. The results of kinetic experiments demonstrated that adsorption of DOM by Fh was significant and rapid. The kinetic adsorption data can be expressed by the pseudo-second-order equation, indicating that the adsorption step might be the rate-limiting step.