Modeling competitive cation exchange of aromatic amines in water-saturated soils

Environ Sci Technol. 2001 Jul 1;35(13):2727-33. doi: 10.1021/es001654a.

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 models--the two-site (TS) and distributed parameter (DP) models--were modified to predict competition. These models assume instantaneous equilibrium of the following reversible processes: (i) acid dissociation of the protonated organic base (BHaq+) in the aqueous phase; (ii) ion exchange on the soil between the protonated organic base and inorganic divalent cations (Daq2+ = Caaq2+ + Mgaq2+); 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 (rho) that relates the ion-exchange association constant (KBH) probability density distribution functions of the two compounds. The value of rho 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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • 1-Naphthylamine / chemistry
  • Amines / chemistry*
  • Aniline Compounds / chemistry
  • Carcinogens / chemistry
  • Cations / chemistry
  • Models, Theoretical*
  • Soil Pollutants / analysis*
  • Water Pollutants, Chemical / analysis*

Substances

  • Amines
  • Aniline Compounds
  • Carcinogens
  • Cations
  • Soil Pollutants
  • Water Pollutants, Chemical
  • 1-Naphthylamine
  • aniline