Anomalous Reactive Transport in the Framework of the Theory of Chromatography

The anomalous reactive transport considered here is the migration of contaminants through strongly sorbing permeable media without significant retardation. It has been observed in the case of heavy metals, organic compounds, and radionuclides, and it has critical implications on the spreading of contaminant plumes and on the design of remediation strategies. Even in the absence of the well-known fast migration pathways, associated with fractures and colloids, anomalous reactive transport arises in numerical simulations of reactive flow. It is due to the presence of highly pH-dependent adsorption and the broadening of the concentration front by hydrodynamic dispersion. This leads to the emergence of an isolated pulse or wave of a contaminant traveling at the average flow velocity ahead of the retarded main contamination front. This wave is considered anomalous because it is not predicted by the classical theory of chromatography, unlike the retardation of the main contamination front. In this study, we use the theory of chromatography to study a simple pH-dependent surface complexation model to derive the mathematical framework for the anomalous transport. We analyze the particular case of strontium (Sr2+) transport and define the conditions under which the anomalous transport arises. We model incompressible one-dimensional (1D) flow through a reactive porous medium for a fluid containing four aqueous species: H+, Sr2+, Na+, and Cl−. The mathematical problem reduces to a strictly hyperbolic 2 × 2 system of conservation laws for effective anions and Sr2+, coupled through a competitive Langmuir isotherm. One characteristic field is linearly degenerate while the other is not genuinely nonlinear due to an inflection point in the pH-dependent isotherm. We present the complete set of analytical solutions to the Riemann problem, consisting of only three combinations of a slow wave comprising either a rarefaction, a shock, or a shock–rarefaction with fast wave comprising only a contact discontinuity. Highly resolved numerical solutions at large Péclet numbers show excellent agreement with the analytic solutions in the hyperbolic limit. In the Riemann problem, the anomalous wave forms only if: hydrodynamic dispersion is present, the slow wave crosses the inflection locus, and the effective anion concentration increases along the fast path.