title: Modeling sorption of anionic surfactants onto sediment materials: an a priori approach for perfluoroalkyl surfactants and linear alkylbenzene sulfonates.
abstract: A mechanistically derived model predicting the sorption of anionic surfactants to sediments was developed and evaluated for three classes of surfactants: perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and linear alkylbenzene sulfonates. The model includes both hydrophobic and electrostatic components and estimates the contribution of each to the sediment-water distribution coefficient (Kd) using Gibbs free energy terms. The hydrophobic free energy term was calculated from the aqueous solubilities of non-charged alkylbenzene or perfluoroalkane analogs and prior observations of increases in Kd values with increasing chain lengths. The electrostatic term was calculated from aqueous solution measurements using the non-ideal competitive adsorption Donnan (NICA-Donnan) model. The NICA-Donnan calculations were performed using parameters previously derived for generic humic acids. These two terms were coupled by multiplying by the fraction of organic carbon in the sediment, foc, and a single fitting parameter, Faccess, the volumetric fraction of organic carbon accessible to the sorbing surfactant. The combined model accurately predicted the sediment-water distribution coefficients for all three classes of anionic surfactants. In its current formulation, the model was unable to capture the slight degree of isotherm nonlinearity observed for these surfactants.
authors.affiliation: Department of Civil and Environmental Engineering, Stanford University, Stanford, California 94305-4020, USA.
authors.forename: Christopher P
authors.initials: CP
authors.lastname: Higgins
authors.forename: Richard G
authors.initials: RG
authors.lastname: Luthy
mesh_terms: D000327:Adsorption; D017738:Alkanesulfonic Acids / Q000737:chemistry*; D005466:Fluorocarbons / Q000737:chemistry*; D019015:Geologic Sediments / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D008956:Models, Chemical; D012989:Soil Pollutants / Q000737:chemistry; D013501:Surface-Active Agents / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry
chemical_list: D017738:Alkanesulfonic Acids; D005466:Fluorocarbons; D012989:Soil Pollutants; D013501:Surface-Active Agents; D014874:Water Pollutants, Chemical