Nonlinear Chlorinated Solvent Sorption Impedes Remediation in Sedimentary Aquifers

Abstract:

A ‘tailing’ pattern of rapid initial contaminant concentration decline followed by sustained release at a lower concentration is commonly produced by active remediation strategies. The ability of aquitard layers to cause this pattern is recognized. However, we hypothesize that nonlinear sorption combined with intragranular diffusion and mass storage within coarse, porous grains, can also cause tailing. Our project combines laboratory measurements of the equilibrium sorption isotherm for trichloroethene (TCE), release measurements from granular samples, and simulations of retarded intragranular diffusion. A novel aspect of our study is that we are examining a sample containing condensed kerogen as the primary form of organic matter on the impact of TCE mass storage, uptake and release rates. The kerogen-containing marine sedimentary rock used in our study is representative of the source rock of the surficial glacial aquifers in the southern Ontario, Canada region. The fact that energy producing shale units occur within the regional stratigraphic sequences indicates the high level of thermal maturation of the kerogen that comprises the sorbent for TCE in these samples. The equilibrium sorption isotherm spans nearly five orders of magnitude in aqueous concentration and is nonlinear. Preliminary comparisons between the mass release curve for grains equilibrated with a high TCE aqueous concentration (ca. 1000 mg/L) show that the physically-based model, which represents release controlled by intragranular diffusion with nonlinear local equilibrium sorption, provides a reasonable fit to the observed data with modest adjustment of the independently determined parameters. Additional experiments documenting TCE release from samples equilibrated at different initial aqueous concentrations and of different grain sizes will also be evaluated using the model and the results compared. Through extending simulations to the field scale, our results will contribute to a general understanding of the importance of the subject processes in sustaining contaminant plumes and will inform more effective remediation.