Establishing a physical and chemical framework for Amorphous Calcium Carbonate (ACC) biomineralization

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Virginia Tech

Recent advances in high-resolution analytical methods have brought about a paradigm shift in our understanding of how crystalline materials are formed. The scientific community now recognizes that many earth materials form by multiple pathways that involve metastable intermediates. Biogenic calcium carbonate minerals are now recognized to develop by aggregating molecules or clusters to form amorphous phases that later transform to one or more crystalline polymorphs. Amorphous calcium carbonate (ACC) is now recognized as a precursor to CaCO₃ biominerals in a wide variety of natural environments. Recent studies suggest an ACC pathway may imprint a different set of dependencies from those established for classical growth processes. Previous ACC studies provided important insights, but a quantitative understanding of controls on ACC composition when formed at near-physiological conditions is not established. The Mg content of ACC and calcite is of particular interest as a minor element that is frequently found in final crystalline products in calcified skeletons.

This three-part dissertation investigated biological and well-characterized synthetic ACC using high-energy x-ray methods, Raman spectroscopy, and mechanical tests. The findings establish chemical and physical properties of ACC in the exoskeleton of crustaceans and show Mg and P levels are tuned in the mineral component to optimize exoskeleton function that could be sensitive to ecological or environmental conditions. Calcite and chitin crystallinity exhibit a similar body-part-specific pattern that correlates directly with the mechanical strength of the exoskeleton. Insights from this study suggest precise biological control of ACC chemistry in the to regulate exoskeleton properties. Laboratory measurements using quantitative methods and compositions that approximate the physiological conditions of crustaceans, demonstrate at least two types of ACC are formed by controlling Mg concentration and alkalinity. We also find temporal changes in the short-range ordering of ACC after precipitation that is dependent upon carbonate content. The findings from this study provide a quantitative basis for deciphering relationships between ACC structures, solution chemistry, and the final transformation products under biologically relevant conditions.

Biomineralization, ACC, crustaceans, calcium carbonate, magnesium