Empirically testing vaterite structural models using neutron diffraction and thermal analysis
Abstract
Otoliths, calcium carbonate (CaCO3) ear bones, are among the most commonly used age and growth structures of fishes. Most fish otoliths are comprised of the most dense CaCO3 polymorph, aragonite. Sturgeon otoliths, in contrast, have been characterized as the rare and structurally enigmatic polymorph, vaterite a metastable polymorph of CaCO3. Vaterite is an important material ranging from biomedical to personal care applications although its crystal structure is highly debated. We characterized the structure of sturgeon otoliths using thermal analysis and neutron powder diffraction, which is used non-destructively. We confirmed that while sturgeon otoliths are primarily composed of vaterite, they also contain the denser CaCO3 polymorph, calcite. For the vaterite fraction, neutron diffraction data provide enhanced discrimination of the carbonate group compared to x-ray diffraction data, owing to the different relative neutron scattering lengths, and thus offer the opportunity to uniquely test the more than one dozen crystal structural models that have been proposed for vaterite. Of those, space group P6522 model, a = 7.1443(4)Å , c = 25.350(4)Å , V = 1121.5(2)Å3 provides the best fit to the neutron powder diffraction data, and allows for a structure refinement using rigid carbonate groups.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Environmental Sciences Division
- Wisconsin Dept. of Natural Resources, Oshkosh, WI (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1333067
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 6; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 60 APPLIED LIFE SCIENCES; otolith; vaterite; neutron diffraction; Rietveld refinement; biomaterial; calcium carbonate polymorphs
Citation Formats
Chakoumakos, Bryan C., Pracheil, Brenda M., Koenigs, Ryan, Bruch, Ronald, and Feygenson, Mikhail. Empirically testing vaterite structural models using neutron diffraction and thermal analysis. United States: N. p., 2016.
Web. doi:10.1038/srep36799.
Chakoumakos, Bryan C., Pracheil, Brenda M., Koenigs, Ryan, Bruch, Ronald, & Feygenson, Mikhail. Empirically testing vaterite structural models using neutron diffraction and thermal analysis. United States. https://doi.org/10.1038/srep36799
Chakoumakos, Bryan C., Pracheil, Brenda M., Koenigs, Ryan, Bruch, Ronald, and Feygenson, Mikhail. Fri .
"Empirically testing vaterite structural models using neutron diffraction and thermal analysis". United States. https://doi.org/10.1038/srep36799. https://www.osti.gov/servlets/purl/1333067.
@article{osti_1333067,
title = {Empirically testing vaterite structural models using neutron diffraction and thermal analysis},
author = {Chakoumakos, Bryan C. and Pracheil, Brenda M. and Koenigs, Ryan and Bruch, Ronald and Feygenson, Mikhail},
abstractNote = {Otoliths, calcium carbonate (CaCO3) ear bones, are among the most commonly used age and growth structures of fishes. Most fish otoliths are comprised of the most dense CaCO3 polymorph, aragonite. Sturgeon otoliths, in contrast, have been characterized as the rare and structurally enigmatic polymorph, vaterite a metastable polymorph of CaCO3. Vaterite is an important material ranging from biomedical to personal care applications although its crystal structure is highly debated. We characterized the structure of sturgeon otoliths using thermal analysis and neutron powder diffraction, which is used non-destructively. We confirmed that while sturgeon otoliths are primarily composed of vaterite, they also contain the denser CaCO3 polymorph, calcite. For the vaterite fraction, neutron diffraction data provide enhanced discrimination of the carbonate group compared to x-ray diffraction data, owing to the different relative neutron scattering lengths, and thus offer the opportunity to uniquely test the more than one dozen crystal structural models that have been proposed for vaterite. Of those, space group P6522 model, a = 7.1443(4)Å , c = 25.350(4)Å , V = 1121.5(2)Å3 provides the best fit to the neutron powder diffraction data, and allows for a structure refinement using rigid carbonate groups.},
doi = {10.1038/srep36799},
journal = {Scientific Reports},
number = ,
volume = 6,
place = {United States},
year = {Fri Nov 18 00:00:00 EST 2016},
month = {Fri Nov 18 00:00:00 EST 2016}
}
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Vaterite Crystals Contain Two Interspersed Crystal Structures
journal, April 2013
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- Science, Vol. 340, Issue 6131
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Works referencing / citing this record:
Significance of otolith calcium carbonate crystal structure diversity to microchemistry studies
journal, May 2019
- Pracheil, Brenda M.; George, Robert; Chakoumakos, Bryan C.
- Reviews in Fish Biology and Fisheries, Vol. 29, Issue 3
Otoliths of sub‐adult Lake Sturgeon Acipenser fulvescens contain aragonite and vaterite calcium carbonate polymorphs
journal, April 2019
- Loeppky, Alison R.; Chakoumakos, Bryan C.; Pracheil, Brenda M.
- Journal of Fish Biology, Vol. 94, Issue 5
Synthesis Methods and Favorable Conditions for Spherical Vaterite Precipitation: A Review
journal, April 2019
- Konopacka-Łyskawa, Donata
- Crystals, Vol. 9, Issue 4
Stacking sequence variations in vaterite resolved by precession electron diffraction tomography using a unified superspace model
journal, June 2019
- Steciuk, Gwladys; Palatinus, Lukáš; Rohlíček, Jan
- Scientific Reports, Vol. 9, Issue 1
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Stacking sequence variations in vaterite resolved by precession electron diffraction tomography using a unified superspace model
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