Key factors in the adsorption of natural organic matter to metal (hydr)oxides: Fractionation and conformational change.

Adsorption of natural organic matter (NOM) to mineral surfaces is an important process determining the environmental fate and biogeochemical cycling of many elements. Natural organic matter consists of a heterogeneous mixture of soft and flexible organic molecules. Upon adsorption, size fractionation may occur, as well as changes in molecular conformation. Although very important, these phenomena have been omitted in existing adsorption models. Filling this gap, a novel framework for NOM adsorption to metal (hydr)oxides is presented. Humic acid (HA) was used as an analog for studying experimentally the NOM adsorption to goethite and its size fractionation as a function of pH, ionic strength, and surface loading. Size fractionation was evaluated for adsorption isotherms collected at pH 4 and 6, showing HA molecules of low molar mass were preferentially adsorbed. This phenomenon was incorporated into the new model. Consistent description of the HA adsorption data over the entire range of pH (3-11), ionic strength (2-100 mM), and surface loading (0.1-3 mg m-2) indicated that the spatial distribution of HA molecules adsorbed in the interface is a trade-off between maximizing the interaction of the HA ligands with the oxide surface and minimizing the electrostatic repulsion between HA particles as a result of interfacial crowding. Our advanced consistent framework is able to quantify changes in molar mass and molecular conformation, thereby significantly contributing to an improved understanding of the competitive power of HA for interacting on oxides with other adsorbed small organic acids as well as environmentally important oxyanions, such as phosphate, arsenate, and others.