Knowledge of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) accumulation at the air−water interface is critical to understanding the fate and transport of these substances in subsurface environments. The surface tension of aqueous solutions containing PFOA and PFOS at concentrations ranging from 0.1 to >1000 mg/L and with dissolved solids (i.e., cations and anions) commonly found in groundwater was measured using the Wilhelmy plate method. The surface tensions of solutions containing dissolved solids were lower than those for ultrapure water, indicating an increase in the surface excess of PFOA and PFOS in the presence of dissolved solids. An equation for the surface excess of PFOA and PFOS with total dissolved solids was developed by fitting the measured surface tension values, which ranged from 72.0 to 16.7 mN/m, to the Szyszkowski equation. On the basis of mass distribution calculations for a representative unsaturated, fine-grained soil, up to 78% of the PFOA and PFOS mass will accumulate at the air−water interface, with the remaining mass dissolved in water and adsorbed on the solids.

Experimental and mathematical modeling studies were performed to examine the effects of stabilizing agents on the transport and retention of fullerene nanoparticles (nC(60)) in water-saturated quartz sand. Three stabilizing systems were considered: naturally occurring compounds known to stabilize nanoparticles (Suwannee river humic acid (SRHA) and fulvic acid (SRFA)), synthetic additives used to enhance nanoparticle stability (Tween 80, a nonionic surfactant), and residual contaminants resulting from the manufacturing process (tetrahydrofuran (THF)). The results of column experiments demonstrated that the presence of THF, at concentrations up to 44.5 mg/L, did not alter nC(60) transport and retention behavior, whereas addition of SRHA (20 mg C/L), SRFA (20 mg C/L), or Tween 80 (1000 mg/L) to the influent nC(60) suspensions dramatically increased the mobility of nC(60), as demonstrated by coincidental nanoparticle and nonreactive tracer effluent breakthrough curves (BTCs) and minimal nC(60) retention. When columns were preflushed with surfactant, nC(60) transport was significantly enhanced compared to that in the absence of a stabilizing agent. The presence of adsorbed Tween 80 resulted in nC(60) BTCs characterized by a declining plateau and retention profiles that exhibited hyperexponential decay. The observed nC(60) transport and retention behavior was accurately captured by a mathematical model that accounted for coupled surfactant adsorption-desorption dynamics, surfactant-nanoparticle interactions, and particle attachment kinetics.

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Perfluoroalkyl acids spontaneously concentrate at air–water and non-aqueous phase liquid (NAPL)–water interfaces, which can influence their retention during subsurface transport. This work presents measurements of air– and NAPL–water interfacial tension for synthetic groundwater containing perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorooctanesulfonamide (FOSA), or aqueous film-forming foam (AFFF) formulations at concentrations ranging from 0.1 to greater than 1000 mg/L. The NAPLs tested included dodecane, tetrachloroethylene, and jet fuel. AFFF formulations were less efficient at lowering interfacial tension than PFOA, FPOS, or FOSA substances below 100 mg/L, while above 100 mg/L, these formulations were more effective, achieving tensions of less than 3 mN/m. Infiltration of solutions with such low tension could lead to mobilization of residual NAPL. Equations based on interfacial tension measurements show that concentrations of PFOA, PFOS, and FOSA at the air–water interface were from 2 to 16 times greater than at the NAPL–water interface below 100 mg/L and were 10–50 times greater for AFFF below 20 mg/L. Calculations for unsaturated soil estimate that up to 87% of PFOS mass was at the air–water interface and less than 4% at the dodecane–water interface for bulk-water concentrations below 1 mg/L.