Modeling kinetic non-equilibrium using the first two moments of the residence time distribution

Abstract

A method for simulating field scale transport of kinetically adsorbing solutes is described. The non-equilibrium adsorption is modeled as a birth and death process and is coupled with the particle tracking approach using the first two moments of the distribution of the particle residence time, i.e., the time that a solute particle stays in the liquid phase. A single residence time distribution, regardless of the initial and final phase, is demonstrated to yield an accurate description of chemical kinetics in the vast majority of field scale problems. The first two moments of the residence time distribution are derived as a function of chemical reaction rates and the transport time interval Δt. It is shown that the first moment of the residence time represents a measure of the speed of the chemical reaction relative to the transport time scale Δt which is chosen depending on the velocity field. The second moment of the residence time reflects the relative importance of the chemical kinetics versus local equilibrium conditions for the given transport time step Δt. The simulated spatial moments of the contaminant plume are compared in the one-dimensional case with available analytical solutions to demonstrate the accuracy of the proposed technique. A two-dimensional case for stratified formations is presented to study the transport behavior for heterogeneous velocity fields and variable distribution coefficient, hypothesized as being negatively correlated with hydraulic conductivity. The results show that the enhanced plume spreading and the statistics of the arrival time distribution appear to be more sensitive to the spatially variable distribution coefficient than to the kinetics alone. In fact, the second spatial moment was almost doubled in the case of spatially variable distribution coefficient.