Semi-analytical models for two-dimensional multispecies transport of sequentially degradation products influenced by rate-limited sorption subject to arbitrary time-dependent inlet boundary conditions

Abstract

Most of the semi-analytical and analytical models employed to depict multidimensional, multispecies transport of sequentially degrading reaction products are built upon solving a set of coupled advection-dispersion equations (ADEs). Within these equations, sorption is considered as being equilibrium-controlled. However, it has been demonstrated that more realistic predictions of the transport of contaminants in the groundwater could be obtained by the use of a rate-limited sorption process instead of an equilibrium sorption assumption. This study is thus designed to devise semi-analytical models for the two-dimensional multispecies transport of a chemical mixture comprised of a parent compound and its degradation-daughter products which is influenced by rate-limited sorption subject to arbitrary time-dependent inlet boundary conditions. Three integral transforms are applied to generate a set of linear algebraic equations (AEs) resulting from the reductions of the ADEs. The contaminant concentration of each species is calculated by solving these AEs and then retransforming the solutions back to the original time-space domain. The simulation results obtained with our newly developed semi-analytical model are nearly identical to those generated using a numerical model based on the Laplace transform finite difference (LTFD) method. This confirms the validity of the new semi-analytical model. An investigation of the effect of rate-limited sorption on the migration of the contaminant plume is carried out using various time-dependent inlet boundary conditions. The sorption rate values vary from low to high, specifically, 0.05, 0.5, 5, and 50 years−1. The results show that the predicted concentrations of all contaminants within in the decay chain decrease as the sorption rate constant increases, for both constant and exponentially time-dependent boundary sources. However, under pulse loading boundary conditions, the concentrations of the later degradation products tend to increase with the sorption rate constant. The semi-analytical models created in this study, allow for different inlet boundary conditions, so can be utilized to simulate the transport of sequentially degrading reaction products. This greater accuracy makes them useful for many applications.