Experimental and Particle-Tracking Model Analysis of Anomalous Transport and Sorption of Nickel in Natural Soil Columns

Nickel migration measured in laboratory-scale, natural soil column experiments is shown to display anomalous (non-Fickian) transport and non-equilibrium adsorption and desorption patterns. Similar experiments using a conservative tracer also exhibit anomalous behavior. In parallel batch experiments, adsorption and desorption isotherms demonstrate hysteresis, indicating some permanent adsorption. While adsorption is described by the Langmuir isotherm, equilibrium concentrations are higher than those predicted by the same model for desorption. Furthermore, batch and flow-through column experiments show the occurrence of ion exchange of nickel with magnesium and potassium in the soil; aluminum and other ion concentrations are also affected by the presence of nickel. Strong retention of nickel during transport in soil columns leads to delayed initial breakthrough (~40 pore volumes), slow increase in concentration, and extended concentration tailing at long times. Standard models, including two-site non-equilibrium formulations, fail to capture these features quantitatively. We describe the mechanisms of transport and adsorption/desorption in terms of a continuous time random walk (CTRW) model, and use a particle tracking formulation to simulate the nickel migration in the column. This approach allows us to capture the non-Fickian transport and the subtle local effects of adsorption and desorption. The model uses transport parameters estimated from the conservative tracer and, as a starting point, adsorption/desorption parameters based on the batch experiments to account for the reactions. It is shown that the batch parameters under-estimate the actual adsorption in the column. The CTRW particle tracking model is shown to capture both the full evolution of the measured breakthrough curve and the measured spatial concentration profile. Analysis of these results provides further understanding of the interaction and dynamics between transport and sorption mechanisms in natural soil.