Effective diffusion coefficients of DNAPL waste components in saturated low permeability soil materials

Diffusion is regarded as the dominant transport mechanism into and out of low permeable subsurface lenses and layers in the subsurface. But, some reports of mass storage in such zones are higher than what might be attributable to diffusion, based on estimated diffusion coefficients. Despite the importance of diffusion to efforts to estimate the quantity of residual contamination in the subsurface, relatively few studies present measured diffusion coefficients of organic solutes in saturated low permeability soils. This study reports the diffusion coefficients of a trichloroethylene (TCE), and an anionic surfactant, Aerosol OT (AOT), in water-saturated silt and a silt-montmorillonite (25:75) mixture, obtained using steady-state experiments. The relative diffusivity ranged from 0.11 to 0.17 for all three compounds for the silt and the silt-clay mixture that was allowed to expand. In the case in which the swelling was constrained, the relative diffusivity was about 0.07. In addition, the relative diffusivity of 13C-labeled TCE through a water saturated silt-clay mixture that had contacted a field dense non-aqueous phase liquid (DNAPL) for 18months was measured and equaled 0.001. These experimental results were compared with the estimates generated using common correlations, and it was found that, in all cases, the measured diffusion coefficients were significantly lower than the estimated. Thus, the discrepancy between mass accumulations observed in the field and the mass storage that can attributable to diffusion may be greater than previously believed. •Average relative diffusivity for TCE in silt–montmorillonite mixture (75:25) equaled 0.14.•Relative diffusivity for TCE in sample contacted for eighteen months with a field DNAPL equaled 0.001.•Commonly used estimation techniques overestimated the measured relative diffusivities with a minimum relative error of 300%.