in situ Calcite Precipitation for Contaminant Immobilization Yoshiko Fujita (Yoshiko.fujita@inl.gov) (Idaho National Laboratory, Idaho Falls, Idaho, USA) Robert W. Smith (University of Idaho-Idaho Falls, Idaho Falls, Idaho, USA) Subsurface radionuclide and trace metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE’s greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide strontium-90, is co-precipitation in calcite. Calcite, a common mineral in the arid western U.S., can form solid solutions with trace metals. The rate of trace metal incorporation is susceptible to manipulation using either abiotic or biotic means. We have previously demonstrated that increasing the calcite precipitation rate by stimulating the activity of urea hydrolyzing microorganisms can result in significantly enhanced Sr uptake. Urea hydrolysis causes the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity, and also by liberating the reactive cations from the aquifer matrix via exchange reactions involving the ammonium ion derived from urea: H2NCONH2 + 3H2O ? 2NH4+ + HCO3- + OH- urea hydrolysis >X:2Ca + 2NH4+ ? 2>X:NH4 + Ca2+ ion exchange Ca2+ + HCO3- + OH- ? CaCO3(s) + H2O calcite precipitation where >X: is a cation exchange site on the aquifer matrix. This contaminant immobilization approach has several attractive features. Urea hydrolysis is catalyzed by the urease enzyme, which is produced by many indigenous subsurface microorganisms. Addition of foreign microbes is unnecessary. In turn the involvement of the native microbes and the consequent in situ generation of reactive components in the aqueous phase (e.g., carbonate and Ca or Sr) can allow dissemination of the reaction over a larger volume and/or farther away from an amendment injection point, as compared to direct addition of the reactants at a well (which can lead to clogging). A final particularly attractive characteristic of this approach is its long-term sustainability; the remediation scheme is geared toward environments that are already saturated with respect to calcite, and in such systems the bulk of any newly precipitated calcite will remain stable once engineered manipulations cease. This means that the co-precipitated contaminants will be effectively sequestered over the long term. We are currently conducting integrated field, laboratory, and computational research to evaluate a) the relationships between urea hydrolysis rate, calcite precipitation rate, and trace metal partitioning under environmentally relevant conditions; and b) the coupling between flow/flux manipulations and calcite precipitate distribution and metal uptake. We are also assessing the application of geophysical and molecular biological tools to monitor the relevant chemical and physical processes. The primary emphasis is on field-scale processes, with the laboratory and modeling activities designed specifically to support the field studies. Field experiments are being conducted in perched water (vadose zone) at the Vadose Zone Research Park (VZRP) at the Idaho National Laboratory; the VZRP provides an uncontaminated setting that is an analog of the 90Sr-contaminated vadose zone at the Idaho Nuclear Technology and Engineering Center. A summary of results to date will be presented.
