skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  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 Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); 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.
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. doi:10.1021/jacs.5b07931.
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. doi:10.1021/jacs.5b07931.
@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 = {2015},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/jacs.5b07931

Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Aqueous ball milling of nacre constituents facilitates directional self-assembly of aragonite nanoparticles of the gastropod Haliotis glabra
journal, November 2017

  • Lemloh, Marie-Louise; Verch, Andreas; Weiss, Ingrid M.
  • Journal of The Royal Society Interface, Vol. 14, Issue 136
  • DOI: 10.1098/rsif.2017.0450

In vivo characterization of bivalve larval shells: a confocal Raman microscopy study
journal, April 2018

  • Ramesh, Kirti; Melzner, Frank; Griffith, Andrew W.
  • Journal of The Royal Society Interface, Vol. 15, Issue 141
  • DOI: 10.1098/rsif.2017.0723

Nanoindentation on the bio-inspired high-performance nature composite by molecular dynamics method
journal, January 2019

  • Masir, Amin Nouroozi; Darvizeh, Abolfazl; Zajkani, Asghar
  • Advanced Composites Letters, Vol. 28
  • DOI: 10.1177/0963693519860162

Amorphous calcium carbonate particles form coral skeletons
journal, August 2017

  • Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 37
  • DOI: 10.1073/pnas.1707890114

Aqueous ball milling of nacre constituents facilitates directional self-assembly of aragonite nanoparticles of the gastropod Haliotis glabra
journal, November 2017

  • Lemloh, Marie-Louise; Verch, Andreas; Weiss, Ingrid M.
  • Journal of The Royal Society Interface, Vol. 14, Issue 136
  • DOI: 10.1098/rsif.2017.0450

In vivo characterization of bivalve larval shells: a confocal Raman microscopy study
journal, April 2018

  • Ramesh, Kirti; Melzner, Frank; Griffith, Andrew W.
  • Journal of The Royal Society Interface, Vol. 15, Issue 141
  • DOI: 10.1098/rsif.2017.0723

Coherently aligned nanoparticles within a biogenic single crystal: A biological prestressing strategy
journal, December 2017

  • Polishchuk, Iryna; Bracha, Avigail Aronhime; Bloch, Leonid
  • Science, Vol. 358, Issue 6368
  • DOI: 10.1126/science.aaj2156

Nanoindentation on the bio-inspired high-performance nature composite by molecular dynamics method
journal, January 2019

  • Masir, Amin Nouroozi; Darvizeh, Abolfazl; Zajkani, Asghar
  • Advanced Composites Letters, Vol. 28
  • DOI: 10.1177/0963693519860162