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Title: Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

Abstract

Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. Here, the chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of the interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO 3 biomineralization.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [3];  [3];  [5];  [4];  [6];  [2]
  1. Univ. of California, Davis, CA (United States); Australian National Univ., Acton, ACT (Australia)
  2. Univ. of Washington, Seattle, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Univ. of California, Davis, CA (United States)
  5. Lamont-Doherty Earth Observatory of Columbia Univ., Palisades, NY (United States)
  6. Univ. of California, Davis, CA (United States); Oregon State Univ., Corvallis, OR (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1330468
Alternate Identifier(s):
OSTI ID: 1339818
Report Number(s):
PNNL-SA-112579
Journal ID: ISSN 0027-8424; 48564; KP1704020
Grant/Contract Number:  
AC05-76RL01830; 48564
Resource Type:
Journal Article: Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 46; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory; biomineralization; templating; foraminifera; geochemistry; paleoceanography

Citation Formats

Branson, Oscar, Bonnin, Elisa A., Perea, Daniel E., Spero, Howard J., Zhu, Zihua, Winters, Maria, Honisch, Barbel, Russell, Ann D., Fehrenbacher, Jennifer S., and Gagnon, Alexander C. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation. United States: N. p., 2016. Web. doi:10.1073/pnas.1522864113.
Branson, Oscar, Bonnin, Elisa A., Perea, Daniel E., Spero, Howard J., Zhu, Zihua, Winters, Maria, Honisch, Barbel, Russell, Ann D., Fehrenbacher, Jennifer S., & Gagnon, Alexander C. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation. United States. doi:10.1073/pnas.1522864113.
Branson, Oscar, Bonnin, Elisa A., Perea, Daniel E., Spero, Howard J., Zhu, Zihua, Winters, Maria, Honisch, Barbel, Russell, Ann D., Fehrenbacher, Jennifer S., and Gagnon, Alexander C. Fri . "Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation". United States. doi:10.1073/pnas.1522864113.
@article{osti_1330468,
title = {Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation},
author = {Branson, Oscar and Bonnin, Elisa A. and Perea, Daniel E. and Spero, Howard J. and Zhu, Zihua and Winters, Maria and Honisch, Barbel and Russell, Ann D. and Fehrenbacher, Jennifer S. and Gagnon, Alexander C.},
abstractNote = {Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. Here, the chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of the interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO3 biomineralization.},
doi = {10.1073/pnas.1522864113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 46,
volume = 113,
place = {United States},
year = {Fri Oct 28 00:00:00 EDT 2016},
month = {Fri Oct 28 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1073/pnas.1522864113

Citation Metrics:
Cited by: 4 works
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Works referenced in this record:

The Initial Stages of Template-Controlled CaCO3 Formation Revealed by Cryo-TEM
journal, March 2009

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