Modeling nonlinear sorption of alcohol ethoxylates to sediment: the influence of molecular structure and sediment properties.

The nonlinear sorption of individual alcohol ethoxylate (AE) homologues was studied as a function of the chemical structure of AE and properties of six marine sediments and three clay minerals. All sorption data for both sediments and clays are well described by a dual-mode model, combining a Langmuir and linear sorption term. The nonlinear isotherms of a single homologue on different substrates almost overlap when sorbed concentrations are expressed per specific surface area. Below and above the Langmuir maximum capacity, isotherms approach linearity. Accordingly, it is demonstrated for nine individual AE that the two linear sorption coefficients for the clay mineral illite are predictive within a factor of two for a North Sea sediment. The linear sorption term at high concentrations is likely related to bilayer formation on the mineral surfaces, for both clays and sediments. Adsorption and bilayer formation to mineral surfaces dominate the sorption behavior of most AE homologues to the tested marine sediments. The two fitted sorption coefficients correlate well with the polar and nonpolar chain lengths of the AE. The enhanced nonlinearity of isotherms for AE with longer ethoxylate chains is explained by both an increasing adsorption coefficient and a decreasing bilayer formation affinity with additional ethoxylate units.