Impact of mineral micropores on transport and fate of organic contaminants: a review.

Nanometer-scale pores are abundant in porous geological media (soils, sediments, and aquifer materials), and may account for over >90% of total mineral surface areas. Sorption of organic contaminants in mineral micropores (<2 nm) plays a key role in controlling their fate and transport when the porous geological media have very low organic carbon contents (<0.1%). Significant adsorption of hydrophobic organic contaminants could only occur in the hydrophobic micropore spaces because of the strong competition from water. The rate of desorption from micropores is very slow due to hindered diffusion, resulting in distinct two-stage desorption behavior for microporous solids. Size exclusion effect prevents micropore-sorbed contaminants from being accessed by microorganisms and their extracellular enzymes, thus reducing their bioavailability and biodegradation rates. Results from recent studies indicate that sorption in micropores can also inhibit abiotic degradation of reactive contaminants by protecting them in confined spaces with little reactive water, slowing down hydrolysis and other water-mediated transformations. As a result of the inhibitory effect on abiotic and biotic transformations, and the slow desorption due to hindered diffusion, sorption in hydrophobic micropores of porous geological media can cause preservation of anthropogenic organic contaminants in the subsurface and may increase their persistence to the time scale of geological ages under appropriate conditions. From a practical perspective, understanding the role of mineral micropores is important in assessing the long-term ecotoxicological risk of organic contaminants in the subsurface and designing remediation strategies.