Predicting the Precipitation of Mineral Phases in Permeable Reactive Barriers

Abstract

The working lifetime of permeable reactive barriers (PRBs) using Fe⁰ as the reactive media is limited by precipitation of secondary minerals, due to reaction of groundwater with Fe⁰. Since PRBs are emplaced at sites with widely differing groundwater chemistry, the suite of minerals that precipitate, as well as the rate of their formation, can vary widely. Using plausible phases obtained from field PRBs, the study shows that chemical equilibrium modeling can correctly predict the amounts of precipitates formed, based on the thermodynamic properties of Fe⁰ and groundwater constituents. These predictions were compared to the results from the solid phase analysis from a field column experiment and from a field-installed PRB at Y-12 Plant, Oak Ridge, TN. Using the column chemical data molar distributions of the precipitates along the flow path were modeled. The maximum precipitation at the Fe⁰-sand interface at the influent end was predicted, where pore water showed high saturation index (SI) with respect to calcite and iron (oxyhydr)oxide. In the absence of flow information, the field sampling data were used to construct an SI-pH diagram, from which the extent of reaction with Fe⁰, the potential for precipitate buildup, and relative residence time for the pore water were identified. Kinetic and heterogeneous flow effects were also discussed. To illustrate the application of chemical equilibrium modeling to the design and planning phase of PRBs, groundwater data from four PRB sites were analyzed. The analysis shows that up to 0.63 cm3/L solid could form in pore water using an average Fe⁰ dissolution rate, leading to severe clogging of Fe⁰ medium over a 10-yr period of operation.