Study of the Interaction of Eu³⁺ with Microbiologically Induced Calcium Carbonate Precipitates using TRLFS

The microbial induced biomineralization of calcium carbonate using the ureolytic bacterium Sporosarcina pasteurii in the presence of trivalent europium, a substitute for trivalent actinides, was investigated by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and a variety of physicochemical techniques. Results showed that the bacterial-driven hydrolysis of urea provides favorable conditions for CaCO₃ precipitation and Eu³⁺ uptake due to subsequent increases in NH₄⁺ and pH in the local environment. Precipitate morphologies were characteristic of biogenically formed CaCO₃ and consistent with the respective mineral phase compositions. The formation of vaterite with some calcite was observed after 1 day, calcite with some vaterite after 1 week, and pure calcite after 2 weeks. The presence of organic material associated with the mineral was also identified and quantified. TRLFS was used to track the interaction and speciation of Eu³⁺ as a molecular probe with the mineral as a function of time. Initially, Eu³⁺ is incorporated into the vaterite phase, while during CaCO₃ phase transformation Eu³⁺ speciation changes resulting in several species incorporated in the calcite phase either substituting at the Ca²⁺ site or in a previously unidentified, low-symmetry site. Comparison of the biogenic precipitates to an abiotic sample shows mineral origin can affect Eu³⁺ speciation within the mineral.