Accumulation of DNAPL waste in subsurface clayey lenses and layers

Chlorinated solvents like trichloroethylene (TCE) and tetrachloroethylene (PCE) are prevalent groundwater contaminants being detected more than half of the Superfund Sites. They are introduced into the subsurface due to improper disposal of hazardous wastes containing these chlorinated dense non-aqueous phase liquids (DNAPL). DNAPL wastes sink in the subsurface and form pools on clay layers. Further transport into the underlying clay layer is dominated by diffusion due to the low permeability of these soils and results in accumulation of contaminants therein overtime through diffusion. However, field evidence reported that mass storage of solvents in such zones was higher than what can be attributed to simple diffusion. To evaluate this finding, mass storage of TCE in a hypothetical aquitard after 30 years of diffusion was calculated. The diffusion coefficient reported in the field study resulted in mass storage of 137.7 g in this hypothetical aquitard whereas the mass calculated using the measured diffusion coefficient of TCE from pure solvent into water-saturated clayey soil was 25-65% of it (35.0-89.4 g). The calculated mass storage was even lower (8.2 g) if the measured diffusion coefficient of TCE from DNAPL waste into waste-contacted soil was used. So, mass of TCE accumulated through sole diffusion was not able to explain the one observed in the field. This excess mass in the field might be the mass of DNAPL entered into the cracks which were reported to form in clay layers as a result of the direct contact between water saturated clay and DNAPL waste. Mass of TCE in the cracks was calculated using reported average crack size and an assumed crack depth, and it appeared that cracks filled with DNAPL could increase the stored mass up to a minimum of 334 g which could easily account for the enhanced mass storage observed in the field.