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Mechanism of enhanced strontium uptake into calcite via an amorphous calcium carbonate (ACC) crystallisation pathway

DOI: 10.1021/acs.cgd.6b01599 DOI Help

Authors: Janice L. Littlewood (University of Leeds) , Samuel Shaw (University of Manchester) , Caroline L. Peacock (University of Leeds) , Pieter Bots (University of Manchester) , Divyesh Trivedi (National Nuclear Laboratories) , Ian T. Burke (University of Leeds)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Crystal Growth & Design

State: Published (Approved)
Published: January 2017
Diamond Proposal Number(s): 8269

Abstract: Calcite formation via an amorphous calcium carbonate (ACC) precursor phase potentially offers a method for enhanced incorporation of incompatible trace metals, including Sr2+. In batch crystallisation experiments where CaCl2 was rapidly mixed with Na2CO3 solutions the Sr2+ : Me2+ ratio was varied from 0.001 to 0.1; and, the pathway of calcite precipitation was directed by either the presence or absence of high Mg2+ concentrations (i.e. using a Mg2+ : total Me2+ ratio of 0.1). In the Mg-free experiments crystallisation proceeded via ACC → vaterite → calcite and average Kd Sr values were between 0.44-0.74. At low Sr2+ concentrations (Sr2+ : Me2+ ratio ≤ 0.01) EXAFS analysis revealed that the Sr2+ was incorporated into calcite in the 6 fold coordinate Ca2+ site. However, at higher Sr2+ concentrations (Sr2+ : Me2+ ratio = 0.1), Sr2+ was incorporated into calcite in a 9-fold site with a local coordination similar to Ca2+ in aragonite, but calcite-like at longer distances (i.e. > 3.5 Å). In the high-Mg experiments the reaction proceeded via an ACC → calcite pathway with higher Kd Sr of 0.90-0.97 due to the presence of Mg2+ stabilising the ACC phase and promoting rapid calcite nucleation in conjunction with higher Sr2+ incorporation. Increased Sr2+ concentrations also coincided with higher Mg2+ uptake in these experiments. Sr2+ was incorporated into calcite in a 9-fold coordinate site in all the high-Mg experiments regardless of initial Sr2+ concentrations, likely as a result of very rapid crystallisation kinetics and the presence of smaller Mg2+ ions compensating for the addition of larger Sr2+ ions in the calcite lattice. These experiments show that the enhanced uptake of Sr2+ ions can be achieved by calcite precipitation via ACC, and may offer a rapid, low temperature, low-cost, method for removal of several incompatible Me2+ ions (e.g. Pb2+, Ba2+, Sr2+) during effluent treatment.

Subject Areas: Earth Science, Chemistry

Instruments: B18-Core EXAFS

Other Facilities: European Synchrotron Radiation Source