Modeling the effects of concentration history on the slow desorption of trichloroethene from a soil at 100% relative humidity.

To determine the effects of concentration history on slow sorption processes, desorption kinetic profiles for trichloroethene (TCE) were measured for a soil at 100% relative humidity subject to different exposure concentrations and exposure times. Exposure concentrations ranged from 1% to 80% of the saturation vapor pressure (Ps) for TCE, and exposure times (i.e., time allowed for sorption before desorption begins) ranged from 1 to 96 days. A spherical diffusion model based on a gamma distribution of sorption rates and a gamma distribution of desorption rates was developed and applied to the data. At 80% P/Ps, the entire gamma distributions of sorption and desorption rates were available for TCE. In accordance with a micropore filling mechanism, the fraction of these distributions available for TCE sorption decreased with decreasing P/Ps. Experimental results are consistent with a micropore-filling mechanism, where the amount of slow desorbing mass decreased with decreasing exposure time, and the fraction of slow desorbing sites filled decreased with decreasing exposure concentration. Simulation results suggest that diffusion limits the rates that micropores fill, and that rates of sorption and desorption for soil contaminated at smaller values of P/Ps are, on average, less than those at larger values of P/Ps (i.e., slow desorption rates are a function of exposure concentration). Simulation results also suggest that the model adequately describes the effects of exposure concentration and exposure time on the rates of sorption and desorption, but not on the capacity of the slow sites for TCE. This work is important because contaminant concentrations in the subsurface vary in space and time, and the proposed model represents a new and mechanistically based approach to capture the effects of this heterogeneity on slow desorption.