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

Author:

Schmidt Connor A.,Tambutté EricORCID,Venn Alexander A.ORCID,Zou ZhaoyongORCID,Castillo Alvarez CristinaORCID,Devriendt Laurent S.,Bechtel Hans A.ORCID,Stifler Cayla A.,Anglemyer SamanthaORCID,Breit Carolyn P.,Foust Connor L.,Hopanchuk Andrii,Klaus Connor N.,Kohler Isaac J.ORCID,LeCloux Isabelle M.,Mezera JaidenORCID,Patton Madeline R.ORCID,Purisch Annie,Quach Virginia,Sengkhammee Jaden S.,Sristy TarakORCID,Vattem Shreya,Walch Evan J.,Albéric Marie,Politi Yael,Fratzl Peter,Tambutté SylvieORCID,Gilbert Pupa U.P.A.ORCID

Abstract

AbstractCalcium 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.

Funder

U.S. Department of Energy

NSF | Directorate for Mathematical & Physical Sciences | Division of Materials Research

Publisher

Springer Science and Business Media LLC

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