Nickel migration and retention dynamics in natural soil columns

Nickel migration measured in laboratory-scale, natural soil column experiments is shown to display anomalous (non-Fickian) transport, nonequilibrium adsorption and desorption patterns, and precipitation/dissolution. Similar experiments using a conservative tracer also exhibit anomalous behavior. The occurrence of ion exchange of nickel, mainly with calcium (but also with other soil components), is measured in both batch and flow-through column experiments; adsorption and desorption isotherms demonstrate hysteresis. Strong retention of nickel during transport in soil columns leads to delayed initial breakthrough (approximate to 40 pore volumes), slow increase in concentration, and extended concentration tailing at long times. We describe the mechanisms of transport and retention in terms of a continuous time random walk (CTRW) model, and use a particle tracking formulation to simulate nickel migration in the column. This approach allows us to capture the non-Fickian transport and the subtle local effects of adsorption/desorption and precipitation/dissolution. Consideration also of preferential pathways accounts for the evolution of the measured breakthrough curve and measured spatial concentration profiles. The model uses non-Fickian transport parameters estimated from the conservative tracer and, as a starting point, adsorption/desorption parameters based on batch experiments and a precipitation parameter based on K-sp values. The batch parameters are found to underestimate the actual amount of adsorption. We suggest that the sorption and precipitation/dissolution dynamics, and resulting breakthrough curves, are influenced strongly by preferential pathways; such pathways significantly alter the availability of sorption sites and ion availability for precipitation. Analysis of these results provides further understanding of the interaction and dynamics among transport, precipitation, and sorption mechanisms in natural soil.