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

Journal Article · · Nature Communications
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Abstract Calcium carbonate (CaCO 3 ) 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 CO 2 into solid biominerals. Six crystalline polymorphs of CaCO 3 are known—3 anhydrous: calcite, aragonite, vaterite, and 3 hydrated: ikaite (CaCO 3 ·6H 2 O), monohydrocalcite (CaCO 3 ·1H 2 O, MHC), and calcium carbonate hemihydrate (CaCO 3 ·½H 2 O, 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.

Sponsoring Organization:
USDOE
Grant/Contract Number:
FG02-07ER15899; AC02-05CH11231
OSTI ID:
2315746
Alternate ID(s):
OSTI ID: 2426866
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United Kingdom
Language:
English

References (71)

The formation and transformation mechanism of calcium carbonate in water journal October 1987
Planktic foraminifera form their shells via metastable carbonate phases journal November 2017
The Crystallization of Amorphous Calcium Carbonate is Kinetically Governed by Ion Impurities and Water journal February 2018
The evolution of the marine carbonate factory journal February 2023
Amorphous calcium carbonate transforms into calcite during sea urchin larval spicule growth journal March 1997
Impact of amorphous precursor phases on magnesium isotope signatures of Mg-calcite journal April 2017
Isotopic tracer evidence for the amorphous calcium carbonate to calcite transformation by dissolution–reprecipitation journal September 2015
MEPHISTO spectromicroscope reaches 20 nm lateral resolution journal March 1999
Biomineralization: Integrating mechanism and evolutionary history journal March 2022
Carbonic Anhydrase in the Scleractinian Coral Stylophora pistillata journal September 2008
Pervasive nanoscale deformation twinning as a catalyst for efficient energy dissipation in a bioceramic armour journal March 2014
Growth dynamics and amorphous-to-crystalline phase transformation in natural nacre journal April 2023
Synchrotron infrared nano-spectroscopy and -imaging journal August 2020
The Correlation of Microchemical Properties to Antiwear (AW) Performance in Ashless Thiophosphate Oil Additives journal November 2004
Structural Characterization of the Transient Amorphous Calcium Carbonate Precursor Phase in Sea Urchin Embryos journal July 2006
Effect of seawater carbonate concentration on foraminiferal carbon and oxygen isotopes journal December 1997
X-ray Absorption Near-Edge Structure (XANES) Spectroscopy journal January 2014
Bioinspired structural materials journal October 2014
Magnesium Impurities Decide the Structure of Calcium Carbonate Hemihydrate journal November 2020
Mg/Ca Thermometry in Coral Skeletons journal November 1996
Chemomechanical Properties of Antiwear Films Using X-ray Absorption Microscopy and Nanoindentation Techniques journal August 2004
Trace and major element incorporation into amorphous calcium carbonate (ACC) precipitated from seawater journal December 2020
Local Atomic Order and Infrared Spectra of Biogenic Calcite journal January 2007
Ultrabroadband infrared nanospectroscopic imaging journal May 2014
Anisotropic lattice distortions in biogenic aragonite journal November 2004
Photoemission spectromicroscopy for the biomineralogist book February 2014
Cellular pathways of calcium transport and concentration toward mineral formation in sea urchin larvae journal November 2020
Solid-State Phase Transformation and Self-Assembly of Amorphous Nanoparticles into Higher-Order Mineral Structures journal June 2020
Characterization of unusual MgCa particles involved in the formation of foraminifera shells using a novel quantitative cryo SEM/EDS protocol journal September 2018
Phase transitions in biogenic amorphous calcium carbonate journal April 2012
Full in vivo characterization of carbonate chemistry at the site of calcification in corals journal January 2019
Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate journal September 2010
Biomineral mesostructure journal March 2023
Spherulitic Growth of Coral Skeletons and Synthetic Aragonite: Nature’s Three-Dimensional Printing journal June 2017
Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy journal January 2015
Nanostructured artificial nacre journal May 2003
Oxygen Spectroscopy and Polarization-Dependent Imaging Contrast (PIC)-Mapping of Calcium Carbonate Minerals and Biominerals journal May 2014
Amorphous layer around aragonite platelets in nacre journal August 2005
Marine inspiration journal May 2008
The probing depth of total electron yield in the sub-keV range: TEY-XAS and X-PEEM journal July 2003
Sea Urchin Spine Calcite Forms via a Transient Amorphous Calcium Carbonate Phase journal November 2004
From particle attachment to space-filling coral skeletons journal November 2020
Oxygen isotope fractionation in the CaCO3-DIC-H2O system journal October 2017
Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule journal November 2008
Crystals competing for space journal November 2014
Compensation of charging in X-PEEM: a successful test on mineral inclusions in 4.4Ga old zircon journal December 2003
Transformation kinetics of monohydrocalcite to aragonite in aqueous solutions journal January 2008
Biomimetism and bioinspiration as tools for the design of innovative materials and systems journal April 2005
Mollusc larval shell formation: amorphous calcium carbonate is a precursor phase for aragonite journal August 2002
Binding of Ethanol on Calcite: The Role of the OH Bond and Its Relevance to Biomineralization journal October 2010
Elemental compositions of sea urchin larval cell vesicles evaluated by cryo-STEM-EDS and cryo-SEM-EDS journal January 2023
Ubiquitous macropinocytosis in anthozoans journal February 2020
MEPHISTO: Performance tests of a novel synchrotron imaging photoelectron spectromicroscope journal May 1998
Faster Crystallization during Coral Skeleton Formation Correlates with Resilience to Ocean Acidification journal January 2022
Additives Control the Stability of Amorphous Calcium Carbonate via Two Different Mechanisms: Surface Adsorption versus Bulk Incorporation journal April 2020
An artificial biomineral formed by incorporation of copolymer micelles in calcite crystals journal September 2011
Nanoscale Transforming Mineral Phases in Fresh Nacre journal October 2015
Spatially resolved nanoscale chemical and mechanical characterization of ZDDP antiwear films on aluminum?silicon alloys under cylinder/bore wear conditions journal March 2005
Nanostructure, composition and mechanisms of bivalve shell growth journal November 2008
A multi-technique characterization of ZDDP antiwear films formed on Al (Si) alloy (A383) under various conditions journal February 2007
Tuning hardness in calcite by incorporation of amino acids journal May 2016
Sea surface temperature and salinity reconstruction from coral geochemical tracers journal March 2006
A hydrated crystalline calcium carbonate phase: Calcium carbonate hemihydrate journal January 2019
Calcium carbonate as ikaite crystals in Antarctic sea ice journal April 2008
Evidence for a Liquid Precursor to Biomineral Formation journal September 2021
Declining Coral Calcification on the Great Barrier Reef journal January 2009
Revealing crystalline domains in a mollusc shell single-crystalline prism journal July 2017
Nanoscale Chemical Imaging by Photo‐Induced Force Microscopy: Technical Aspects and Application to the Geosciences journal February 2021
Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization journal June 2003
Amorphous calcium carbonate particles form coral skeletons journal August 2017
A Molecular‐Scale Understanding of Misorientation Toughening in Corals and Seashells journal April 2023