Silicate surface coverage controls quinolone transport in saturated porous media

Abstract

Although silicates are the most common anions in aquatic systems, little is known on the roles they play on the transport of emerging contaminants, such as antibiotics. Using dynamic column experiments, we revealed the controls of Si loadings on goethite (α-FeOOH) coated sands on the transport of a widely used quinolone antibiotic, here focusing on Nalidixic Acid (NA). We find that dynamic flow-through conditions (Darcy velocities of 2.98 cm/h and 14.92 cm/h) sustain monomeric Si species with loadings of up to ~ 0.8 Si/nm² but that oligomeric species can form at the goethite surfaces under static (batch, no-flow conditions). While these monomeric species occupy no more than ~ 22% of the reactive OH groups on goethite, they can effectively suppress NA binding, and therefore enhance NA mobility in dynamic conditions. NA can also bind on goethite when it is simultaneously injected with high concentrations of Si (2000 µM), yet it becomes progressively replaced by Si over time. Combining kinetics and surface complexation modeling, we present a new transport model to account for the stepwise polymerization of Si on goethite and NA transport. Our findings show that dissolved Si, common to natural surface waters, can play a determining role on the surface speciation and transport of antibiotics in the environment.

Keywords: Adsorption; Modeling; Polymerization; Reactive transport; Silicate.