Myriad Mapping of nanoscale minerals reveals calcium carbonate hemihydrate in forming nacre and coral biominerals

Connor A. Schmidt, Eric Tambutté, Alexander A. Venn, Zhaoyong Zou, Cristina Castillo Alvarez, Laurent S. Devriendt, Hans A. Bechtel, Cayla A. Stifler, Samantha Anglemyer, Carolyn P. Breit, Connor L. Foust, Andrii Hopanchuk, Connor N. Klaus, Isaac J. Kohler, Isabelle M. LeCloux, Jaiden Mezera, Madeline R. Patton, Annie Purisch, Virginia Quach, Jaden S. Sengkhammee, Tarak Sristy, Shreya Vattem, Evan J. Walch, Marie Albéric, Yael Politi, Peter Fratzl, Sylvie Tambutté and Pupa U.P.A. Gilbert ()
Additional contact information
Connor A. Schmidt: University of Wisconsin
Eric Tambutté: Centre Scientifique de Monaco
Alexander A. Venn: Centre Scientifique de Monaco
Zhaoyong Zou: Wuhan University of Technology
Cristina Castillo Alvarez: Lawrence Berkeley National Laboratory
Laurent S. Devriendt: Lawrence Berkeley National Laboratory
Hans A. Bechtel: Lawrence Berkeley National Laboratory
Cayla A. Stifler: University of Wisconsin
Samantha Anglemyer: University of Wisconsin
Carolyn P. Breit: University of Wisconsin
Connor L. Foust: University of Wisconsin
Andrii Hopanchuk: University of Wisconsin
Connor N. Klaus: University of Wisconsin
Isaac J. Kohler: University of Wisconsin
Isabelle M. LeCloux: University of Wisconsin
Jaiden Mezera: University of Wisconsin
Madeline R. Patton: University of Wisconsin
Annie Purisch: University of Wisconsin
Virginia Quach: University of Wisconsin
Jaden S. Sengkhammee: University of Wisconsin
Tarak Sristy: University of Wisconsin
Shreya Vattem: University of Wisconsin
Evan J. Walch: University of Wisconsin
Marie Albéric: Laboratoire de chimie de la matière condensée
Yael Politi: Technische Universität Dresden
Peter Fratzl: Max Planck Institute of Colloids and Interfaces
Sylvie Tambutté: Centre Scientifique de Monaco
Pupa U.P.A. Gilbert: University of Wisconsin

Nature Communications, 2024, vol. 15, issue 1, 1-15

Abstract: Abstract Calcium carbonate (CaCO3) is abundant on Earth, is a major component of marine biominerals and thus of sedimentary and metamorphic rocks and it plays a major role in the global carbon cycle by storing atmospheric CO2 into solid biominerals. Six crystalline polymorphs of CaCO3 are known—3 anhydrous: calcite, aragonite, vaterite, and 3 hydrated: ikaite (CaCO3·6H2O), monohydrocalcite (CaCO3·1H2O, MHC), and calcium carbonate hemihydrate (CaCO3·½H2O, CCHH). CCHH was recently discovered and characterized, but exclusively as a synthetic material, not as a naturally occurring mineral. Here, analyzing 200 million spectra with Myriad Mapping (MM) of nanoscale mineral phases, we find CCHH and MHC, along with amorphous precursors, on freshly deposited coral skeleton and nacre surfaces, but not on sea urchin spines. Thus, biomineralization pathways are more complex and diverse than previously understood, opening new questions on isotopes and climate. Crystalline precursors are more accessible than amorphous ones to other spectroscopies and diffraction, in natural and bio-inspired materials.

Date: 2024
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DOI: 10.1038/s41467-024-46117-x

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