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Title: Nanoscale Transforming Mineral Phases in Fresh Nacre

Abstract

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropod shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.

Authors:
 [1];  [1];  [2];  [1];  [3];  [4]
+ Show Author Affiliations
  1. Department of Physics, University of Wisconsin−Madison, 1150 University Avenue, Madison, Wisconsin 53706, United States
  2. Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
  3. Department of Geosciences, Princeton University, Princeton, New Jersey 08544, United States
  4. Department of Physics, University of Wisconsin−Madison, 1150 University Avenue, Madison, Wisconsin 53706, United States, Department of Chemistry, University of Wisconsin−Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States, Radcliffe Institute for Advanced Study, Harvard University, 8 Garden Street, Cambridge, Massachusetts 02138, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); US-Israel Binational Science Foundation (BSF); Harvard Univ. (United States)
Contributing Org.:
Harvard Univ., Cambridge, MA (United States); Princeton Univ., NJ (United States)
OSTI Identifier:
1223142
Alternate Identifier(s):
OSTI ID: 1378600
Grant/Contract Number:  
FG02-07ER15899; AC02-05CH11231; DMR-1105167; BSF-2010065
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 41; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 58 GEOSCIENCES

Citation Formats

DeVol, Ross T., Sun, Chang-Yu, Marcus, Matthew A., Coppersmith, Susan N., Myneni, Satish C. B., and Gilbert, Pupa U. P. A. Nanoscale Transforming Mineral Phases in Fresh Nacre. United States: N. p., 2015. Web. doi:10.1021/jacs.5b07931.
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DeVol, Ross T., Sun, Chang-Yu, Marcus, Matthew A., Coppersmith, Susan N., Myneni, Satish C. B., & Gilbert, Pupa U. P. A. Nanoscale Transforming Mineral Phases in Fresh Nacre. United States. https://doi.org/10.1021/jacs.5b07931
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DeVol, Ross T., Sun, Chang-Yu, Marcus, Matthew A., Coppersmith, Susan N., Myneni, Satish C. B., and Gilbert, Pupa U. P. A. Wed . "Nanoscale Transforming Mineral Phases in Fresh Nacre". United States. https://doi.org/10.1021/jacs.5b07931.
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@article{osti_1223142,
title = {Nanoscale Transforming Mineral Phases in Fresh Nacre},
author = {DeVol, Ross T. and Sun, Chang-Yu and Marcus, Matthew A. and Coppersmith, Susan N. and Myneni, Satish C. B. and Gilbert, Pupa U. P. A.},
abstractNote = {Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropod shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.},
doi = {10.1021/jacs.5b07931},
journal = {Journal of the American Chemical Society},
number = 41,
volume = 137,
place = {United States},
year = {Wed Oct 07 00:00:00 EDT 2015},
month = {Wed Oct 07 00:00:00 EDT 2015}
}
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  • DOI: 10.1038/nmat1263

Rigid Biological Systems as Models for Synthetic Composites
journal, November 2005

Self-organisation of nacre in the shells of Pterioida (Bivalvia: Mollusca)
journal, March 2005

Self-Sharpening Mechanism of the Sea Urchin Tooth
journal, December 2010

  • Killian, Christopher E.; Metzler, Rebecca A.; Gong, Yutao
  • Advanced Functional Materials, Vol. 21, Issue 4
  • DOI: 10.1002/adfm.201001546

X-ray-driven reaction front dynamics at calcite-water interfaces
journal, September 2015

Stabilization of Amorphous Calcium Carbonate in Inorganic Silica-Rich Environments
journal, December 2010

  • Kellermeier, Matthias; Melero-García, Emilio; Glaab, Fabian
  • Journal of the American Chemical Society, Vol. 132, Issue 50
  • DOI: 10.1021/ja106959p

The probing depth of total electron yield in the sub-keV range: TEY-XAS and X-PEEM
journal, July 2003

Stable Amorphous Calcium Carbonate Is the Main Component of the Calcium Storage Structures of the Crustacean Orchestia cavimana
journal, December 2002

  • Raz, Sefi; Testeniere, Olivier; Hecker, Arnaud
  • The Biological Bulletin, Vol. 203, Issue 3
  • DOI: 10.2307/1543569

Precipitation of ACC in liposomes—a model for biomineralization in confined volumes
journal, January 2012

  • Tester, Chantel C.; Wu, Ching-Hsuan; Weigand, Steven
  • Faraday Discussions, Vol. 159
  • DOI: 10.1039/c2fd20088k

Immunogold detection of glycoprotein antigens in sea urchin embryos
journal, June 1989

  • Benson, Nancy C.; Benson, Stephen C.; Wilt, Fred
  • American Journal of Anatomy, Vol. 185, Issue 2-3
  • DOI: 10.1002/aja.1001850210

Exploring the influence of organic species on pre- and post-nucleation calcium carbonate
journal, January 2012

  • Raiteri, Paolo; Demichelis, Raffaella; Gale, Julian D.
  • Faraday Discussions, Vol. 159
  • DOI: 10.1039/c2fd20052j

Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule
journal, November 2008

  • Politi, Y.; Metzler, R. A.; Abrecht, M.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 45
  • DOI: 10.1073/pnas.0806604105
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