A model which includes the transport and retardation mechanisms of advective flow, axial dispersion, liquid-phase mass transfer, diffusion into immobile liquid, and local adsorption equilibrium was developed to describe the migration of nondegradable, organic chemicals through a column of saturated, aggregated soil. A range of simplifying assumptions were explored to assess the relative importance of the various mechanisms. Solutions to the model were either adapted from the literature or derived from mass balances and mass transfer principles. The most general form of the model required the development of numerical solutions which employed orthogonal collocation. Soil column breakthrough predictions in terms of relative concentration as a function of total column pore volumes fed can be characterized by seven independent dimensionless parameters: the Peclet number, the Stanton number, a pore diffusion modulus, a surface diffusion modulus, an adsorbed solute distribution ratio, an immobile fluid solute distribution ratio, and the Freundlich parameter 1/n. For a strongly adsorbed chemical in long soil columns, a fifteen fold decrease of the Peclet number, a fivefold decrease of the Stanton number, or a onefold decrease in either the pore diffusion modulus or the surface diffusion modulus have an equivalent effect on the spreading of the breakthrough curve. The breakthrough curve tends to sharpen for favorably adsorbed chemical species (1/n < 1.0) and spread when adsorption is unfavorable (1/n > 1.0). The movement of chemical is retarded as the solute distribution ratios increase. A sensitivity analysis of model parameters, which were derived from literature correlations, column geometry, soil adsorption isotherms, and breakthrough curves, showed that adsorption capacity, adsorption intensity, and aggregate geometry have the greatest effect on chemical retardation and spreading, while liquid-phase mass transfer has little effect.
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