Modeling the Adsorption and Coagulation of Fulvic Acids on Colloids by Brownian Dynamics Simulations

Abstract

Humic substances (HS) play an important role in the reactivity and transport of colloids in natural environments. In particular, the presence of fulvic acids (FA) in natural waters modifies the interactions between inorganic particles and biopolymers and makes difficult to predict their stability with regard to aggregation processes. In this study, Brownian dynamics (BD) modeling is applied to quantify the interactions between negatively charged FA and (i) a positively charged inorganic particle and (ii) a rigid neutral polysaccharide in aqueous solutions. Hematite and schizophyllan are respectively used as model colloids. Modeling the adsorption of FA at the hematite particle surface and on the polysaccharide is based on van der Waals attractive forces and electrostatic interactions. Possible applications of the model, however, are not restricted to this system and any interaction potential or colloidal particle can be considered. The competition between FA adsorption and FA homocoagulation in solution is studied as function of the solution ionic strength. Results show that, under the conditions used, the amount of adsorbed FA is largely controlled by the solution ionic strength. At low ionic strength the amount of adsorbed FA is limited by the electrostatic repulsion between FA at the colloid surfaces and FA monolayers are formed. By increasing the ionic strength the number of adsorbed FA is found to increase. At a sufficiently large ionic strength, however, FA coagulation in solution may strongly compete with FA adsorption at the hematite and polysaccharide surfaces. FA aggregates then adsorb at the colloid surfaces to form extended and porous structures. Results also suggest that FA adsorption and structure of the adsorbed layers are mainly driven by the complex interplay between electrostatic attractive and repulsive interactions.