Metastable solubility and local structure of amorphous calcium carbonate (ACC)

Mergelsberg, Sebastian T.; De Yoreo, James J.; Miller, Quin RS; Michel, F M.; Ulrich, Robert; Dove, Patricia M.; Dove, Patricia M.

doi:10.1016/j.gca.2020.06.030

Metastable solubility and local structure of amorphous calcium carbonate (ACC)

Journal Article · Sun Nov 15 04:00:00 UTC 2020 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2020.06.030· OSTI ID:1772343

Mergelsberg, Sebastian T. ^[1]; De Yoreo, James J. ^[1]; ^[1]; Michel, F M. ^[2]; Ulrich, Robert ^[3]; Dove, Patricia M. ^[2]; Dove, Patricia M. ^[2]

BATTELLE (PACIFIC NW LAB)
Virginia Polytechnic Institute
Virginia Tech

The properties of amorphous calcium carbonate provide the foundation for understanding mineralization of calcified skeletons but inconsistencies between studies suggest the physical picture is incomplete. This study quantifies the metastable solubility and structure of ACC produced under a series of chemical conditions. Using complementary in situ methods that quantify ACC structure (in situ PDF analysis) in parallel with chemical composition (TGA, ICP-OES), we find two short-range structures are produced that also show distinct morphological differences. Conditions with high carbonate ion concentrations stabilize a Ca-rich ACC with short-range order that is independent of Mg content. In contrast, low carbonate solutions favor Mg-rich ACC with mixed Ca- and Mg-short range order. Measurements of solubility product determined from supersaturated and undersaturated conditions find the distinctive structures are related to solution carbonate activity while solubility is primarily determined by the magnesium content of the solid. Bulk solubility is a composite that concurs with established values. The findings demonstrate the type of ACC that forms is tuned by Mg2+ and CO3-2- concentration and suggest ACC structure, not bulk composition, is a reliable indicator of intermediate phase. This chemical framework also provides a basis for interpreting apparent differences between observations of ACC in synthetic and natural systems that reconciles previous structural studies.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1772343

Report Number(s):: PNNL-SA-160781

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 289

Country of Publication:: United States

Language:: English

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