This paper describes a technique for determining the diffusion coefficient and the distribution coefficient for contaminants using saturated, intact (undisturbed) clayey soil samples. The technique is illustrated with reference to a number of laboratory tests involving advective-diffusive migration of potential contaminants through an intact clayey soil from Sarnia, Ontario. An important aspect of the proposed technique is that the mass of contaminant in the system is kept constant and so significant decrease in source leachate concentration occurs during each test. A simple theoretical model is used to analyze this case and it is shown that this phenomenon can be used to deduce both the diffusion coefficient and the distribution/partitioning coefficient from a single test. Parameters are deduced for a number of salt solutions passing through the clay from the Sarnia area. On the basis of these tests it is suggested that for the Sarnia soil and advective velocities up to the maximum examined (0.035 m/a), mechanical dispersion does not measurably affect the magnitude of the "coefficient of hydrodynamic dispersion" (i.e., there is no significant dispersion). It is also suggested that the effective porosity corresponds to that deduced from the water content of the soil. Key words: contaminant migration, soil, laboratory study, experimental, analysis, diffusion, advection, clays, groundwater.

This paper describes laboratory model tests involving the placement of domestic landfill leachate on top of a layer of saturated undisturbed clayey soil and allowing chemical constituents to migrate into the soil by diffusion only. During the testing period (15 days), samples from the overlying leachate were regularly collected and analyzed for the chemical constituents of interest (i.e., Cl−, Na+, K+, Mg++, and Ca++). At the end of the test, the soil layer was sectioned to determine the pore-water and adsorbed concentration variations with depth for each species. Mathematical model POLLUTE was then used to back-figure both the diffusion coefficient (D) and the adsorption term (ρK). The measured diffusion coefficients at a temperature of 10 °C were determined to be [Formula: see text], [Formula: see text], and [Formula: see text]. The corresponding adsorption terms were [Formula: see text], [Formula: see text], and [Formula: see text].Ca++ and Mg++, originally predominant on the clay exchange sites, were heavily desorbed to accommodate the adsorption of migrating Na+, K+, and possibly NH4+, causing hardness halo effects that the model could not fit. This behaviour corresponds to that commonly observed at domestic waste sites in southern Ontario.The importance of multiple contaminant migration on diffusion rates was assessed by comparing the leachate models with similar models using a variety of single salts dissolved in distilled water as the source solutions. For the single-salt models, all species considered, including Ca++ and Mg++, behaved in a way that could be described by conventional Fickian theory. A comparison of the diffusion and adsorption parameters obtained from the two types of models indicated that for both Na+ and K+, the measured D and ρK from the leachate models were 20 and 60% lower, respectively, than the values obtained from the single-salt models. For Cl−, the diffusion coefficient obtained from the leachate models was 25% higher than that obtained from the single-salt models.For the Sarnia grey soil used, both D and ρK are significantly influenced by the types and amounts of co-diffusing species present in the initial source solutions. Laboratory tests conducted to determine diffusion parameters for use in design should be run with soils and source solutions chemically identical to those expected in the field. Key words: domestic waste leachate, multiple contaminant migration, clayey soil, diffusion, adsorption, laboratory study.

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An experimental investigation of diffusive transport of a nonreactive solute (chloride) in saturated, intact Queenston Shale is described. Laboratory tests were performed by placing distilled water in contact with samples of shale having a high initial concentration of chloride in their pore water. Chloride was then permitted to diffuse out of the shale and into the distilled water reservoir for a period of up to 65 days. At the end of each test, the shale sample was sectioned to determine the variation in chloride pore-water concentration with depth through the sample. Fickian diffusion theory was then used to deduce the diffusion coefficient (D). The experimental diffusion coefficient for chloride at a temperature of 22 ± 1 °C ranged from 1.4 × 10−6 to 1.6 × 10−6 cm2/s, which corresponds to a tortuosity (τ) ranging from 0.095 to 0.108. Based on pore size measurements and consideration of the ionic diameter of hydrated chloride, the "effective porosity" available for chloride diffusion is estimated to be greater than 75% of the total porosity calculated from the moisture content of the shale. Key words: diffusion, chloride, rock matrix, Queenston Shale, laboratory study.

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