Investigation of Strontium Incorporation into Biotically and Abiotically Precipitated-Calcium Calcite Using Secondary Ion Mass Spectrometry

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) complex. A possible approach to their remediation is in situ immobilization by co-precipitation of these elements in authigenic calcite and calcite overgrowths. Microorganisms are known to facilitate the precipitation of calicite; hence the stimulation of biogenic calcite production may offer a means to accelerate co-precipitation of contaminant metals. Strontium is well-known to substitute for Ca in calcium carbonate minerals, and consequently , the uranium fission product 90Sr is a prime candidate for this type of remediation approach. In order to predict the extent and stability of Sr incorporation into calcite precipitated under this bioremediation strategy, it is necessary to understand how much Sr is being incorporated. In these studies, secondary ion mass spectrometry (SIMS) was utilized to characterize the surface chemistry of carbonates generated by bacterial activity in synthetic groundwater containing Ca and Sr. SIMS with sputter depth profiling allows the determination of changes in Sr to Ca ratios with depth in particulate carbonate samples. The sputter depth profiling results can be compared with analysis of the bulk composition by inductively coupled plasma atomic emission spectroscopy (ICP-AES). Results of analyses on carbonates generated by B. pasteurii in synthetic groundwater with initial Ca and Sr concentrations of 80 ppm and 10 ppm, respectively, showed that SIMS could successfully measure ion ratios on the surface and within these particles. ICP-AES data indicated a bulk Sr:Ca ratio of 0.11, and sputtering SIMS data approached this value with increasing depth into the particle. The Sr:Ca ratio however, contrary to what would be expected from precipitation under batch conditions, was lower at the surface of the particles (ca. 0.05) and increased with depth. One possible reason for this phenomenon is re-equilibration with solution conditions after initial fast precipitation induced by the microorganisms. In this presentation, we will evaluate the utility of using SIMS for verifying microbially accelerated production of carbonates for remediation by comparing biotically generated carbonates to carbonates precipitated under abiotic conditions. Funding from DOE-EMSP through DOE Idaho Operations Office Contract DE-AC07-99ID13727 BBWI is gratefully acknowledged.