Modeling Competitive Cation Exchange of Aromatic Amines in Water-Saturated Soils

Abstract

Competitive association to several components of soil through ion exchange processes influences the fate of organic cations in the environment. To examine these processes, the distributions of aniline and 1-aminonaphthalene between aqueous 5 mM CaCl2 solutions and three different Indiana soils were evaluated. Solute ratios (Sr) of aniline to 1-aminonaphthalene of 0.4−4.7 were employed, and the soil solutions ranged in pH from 2.7 to 7.5, with all measurements made 24 h after the introduction of the chemicals to the soils. Two previously proposed equilibrium modelsthe two-site (TS) and distributed parameter (DP) modelswere modified to predict competition. These models assume instantaneous equilibrium of the following reversible processes: (i) acid dissociation of the protonated organic base (B ) in the aqueous phase; (ii) ion exchange on the soil between the protonated organic base and inorganic divalent cations ( = C + M); and (iii) partitioning of the nonionic species of aniline (Baq) to soil organic carbon. The TS model is a general mass action model that does not take into consideration cation exchange site heterogeneity, whereas the DP model considers association constants to these sites to be distributed in a log-normal fashion. To describe competition for cation exchange sites within the DP model, it was necessary to add a correlation coefficient (ρ) that relates the ion-exchange association constant (KBH) probability density distribution functions of the two compounds. The value of ρ is characteristic of each soil. Results indicate that competition has a greater effect at low pH values, where ion exchange is the predominant process. For all cases, these models capture the general trends in the soil−water distribution data of both amines. The DP model also captures the nonlinearity of the 1-aminonaphthalene isotherms at low pH while at the same time capturing the nearly linear isotherms of aniline as a competing organic base.