residue particulate carbon, and spilled organic liquids. Certain manipulations of sorbates or sorbent media may help reveal sorption mechanisms, but mixed sorption phenomena complicate the interpretation of macroscopic data regarding diffusion of HOCs into and out of different matrices and the hysteretic sorption and aging effects commonly observed for geosorbents. Analytical characterizations at the microscale, and mechanistic models derived therefrom, are needed to advance scientific knowledge of HOC sequestration, release, and environmental risk.

The results of experiments designed to identify the process(es) responsible for nonequilibrium sorption of hydrophobic organic chemicals (HOCs) by natural sorbents are reported. The results of experiments performed with natural sorbents were compared to rate data obtained from systems wherein rate-limited sorption was caused by specific sorbate-sorbent interactions. This comparison showed that chemical nonequilibrium associated with specific sorbate-sorbent interactions does not significantly contribute to the rate-limited sorption of HOCs by natural sorbents. Transport-related nonequilibrium was also shown to not be a factor for the systems investigated. Hence, attempts were made to interpret the data in terms of two, sorption-related, diffusive mass-transfer conceptual models: retarded intraparticle diffusion and intraorganic matter diffusion. The analyses provide strong evidence that intraorganic matter diffusion was responsible for the nonequilibrium sorption exhibited by the systems investigated in this paper.

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Miscible-displacement experiments are conducted with perfluorooctanoic acid (PFOA) to determine the contribution of adsorption at the air-water interface to retention during transport in water-unsaturated porous media. Column experiments were conducted with two sands of different diameter at different PFOA input concentrations, water saturations, and pore-water velocities to evaluate the impact of system variables on retardation. The breakthrough curves for unsaturated conditions exhibited greater retardation than those obtained for saturated conditions, demonstrating the significant impact of air-water interfacial adsorption on PFOA retention. Retardation was greater for lower water saturations and smaller grain diameter, consistent with the impact of system conditions on the magnitude of air-water interfacial area in porous media. Retardation was greater for lower input concentrations of PFOA for a given water saturation, consistent with the nonlinear nature of surfactant fluid-fluid interfacial adsorption. Retardation factors predicted using independently determined parameter values compared very well to the measured values. The results showed that adsorption at the air-water interface is a significant source of retention for PFOA, contributing approximately 50-75% of total retention, for the test systems. The significant magnitude of air-water interfacial adsorption measured in this work has ramifications for accurate determination of PFAS migration potential in vadose zones.