Nucleation of metastable aragonite CaCO 3 in seawater
Abstract
Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem" - the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite - which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg-Ca ion concentrations, showing thatmore »
- Authors:
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1235156
- Alternate Identifier(s):
- OSTI ID: 1221824; OSTI ID: 1221825; OSTI ID: 1512178
- Grant/Contract Number:
- FG02-96ER45571; AC02-98CH10886; AC02-05CH11231; EDCBEE
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 112 Journal Issue: 11; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences, Washington, DC (United States)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; nucleation; calcium carbonate; polymorphism; surface energy; solid solution–aqueous solution equilibria; 36 MATERIALS SCIENCE
Citation Formats
Sun, Wenhao, Jayaraman, Saivenkataraman, Chen, Wei, Persson, Kristin A., and Ceder, Gerbrand. Nucleation of metastable aragonite CaCO 3 in seawater. United States: N. p., 2015.
Web. doi:10.1073/pnas.1423898112.
Sun, Wenhao, Jayaraman, Saivenkataraman, Chen, Wei, Persson, Kristin A., & Ceder, Gerbrand. Nucleation of metastable aragonite CaCO 3 in seawater. United States. https://doi.org/10.1073/pnas.1423898112
Sun, Wenhao, Jayaraman, Saivenkataraman, Chen, Wei, Persson, Kristin A., and Ceder, Gerbrand. Wed .
"Nucleation of metastable aragonite CaCO 3 in seawater". United States. https://doi.org/10.1073/pnas.1423898112.
@article{osti_1235156,
title = {Nucleation of metastable aragonite CaCO 3 in seawater},
author = {Sun, Wenhao and Jayaraman, Saivenkataraman and Chen, Wei and Persson, Kristin A. and Ceder, Gerbrand},
abstractNote = {Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem" - the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite - which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg-Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.},
doi = {10.1073/pnas.1423898112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 11,
volume = 112,
place = {United States},
year = {Wed Mar 04 00:00:00 EST 2015},
month = {Wed Mar 04 00:00:00 EST 2015}
}
https://doi.org/10.1073/pnas.1423898112
Web of Science
Works referenced in this record:
Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states
journal, June 2012
- Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag
- Physical Review B, Vol. 85, Issue 23
Control of Aragonite or Calcite Polymorphism by Mollusk Shell Macromolecules
journal, January 1996
- Falini, G.; Albeck, S.; Weiner, S.
- Science, Vol. 271, Issue 5245
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
New metastable form of ice and its role in the homogeneous crystallization of water
journal, May 2014
- Russo, John; Romano, Flavio; Tanaka, Hajime
- Nature Materials, Vol. 13, Issue 7
Theoretical Insights into the Hydrated (10.4) Calcite Surface: Structure, Energetics, and Bonding Relationships
journal, June 2009
- Villegas-Jiménez, Adrián; Mucci, Alfonso; Whitehead, Michael A.
- Langmuir, Vol. 25, Issue 12
In Situ Live Observation of Nucleation and Dissolution of Sodium Chlorate Nanoparticles by Transmission Electron Microscopy
journal, January 2014
- Kimura, Yuki; Niinomi, Hiromasa; Tsukamoto, Katsuo
- Journal of the American Chemical Society, Vol. 136, Issue 5
Thermodynamics of Calcite Growth: Baseline for Understanding Biomineral Formation
journal, October 1998
- Teng, H. H.
- Science, Vol. 282, Issue 5389
First-principles-based calculations of the CaCO 3 -MgCO 3 and CdCO 3 -MgCO 3 subsolidus phase diagrams
journal, March 2003
- Burton, B. P.; Van de Walle, A.
- Physics and Chemistry of Minerals, Vol. 30, Issue 2
Numerical Evidence for bcc Ordering at the Surface of a Critical fcc Nucleus
journal, October 1995
- ten Wolde, Pieter Rein; Ruiz-Montero, Maria J.; Frenkel, Daan
- Physical Review Letters, Vol. 75, Issue 14
Vaterite Crystals Contain Two Interspersed Crystal Structures
journal, April 2013
- Kabalah-Amitai, L.; Mayzel, B.; Kauffmann, Y.
- Science, Vol. 340, Issue 6131
In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways
journal, September 2014
- Nielsen, M. H.; Aloni, S.; De Yoreo, J. J.
- Science, Vol. 345, Issue 6201
Influences of T, S and PCO2 on the pseudo-homogeneous precipitation of CaCO3 from seawater: implications for whiting formation
journal, February 1993
- Morse, John W.; He, Shiliang
- Marine Chemistry, Vol. 41, Issue 4
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
The Multiple Structures of Vaterite
journal, April 2013
- Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.
- Crystal Growth & Design, Vol. 13, Issue 6
Microscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 Solutions
journal, August 2013
- Wallace, A. F.; Hedges, L. O.; Fernandez-Martinez, A.
- Science, Vol. 341, Issue 6148
Stabilization of amorphous calcium carbonate by phosphate rich organic matrix proteins and by single phosphoamino acids
journal, August 2010
- Bentov, Shmuel; Weil, Simy; Glazer, Lilah
- Journal of Structural Biology, Vol. 171, Issue 2
What factors determine cation coordination numbers?
journal, December 1988
- Brown, I. D.
- Acta Crystallographica Section B Structural Science, Vol. 44, Issue 6
Polysaccharide chemistry regulates kinetics of calcite nucleation through competition of interfacial energies
journal, May 2013
- Giuffre, Anthony J.; Hamm, Laura M.; Han, Nizhou
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 23
Ab initio study of thermodynamic, structural, and elastic properties of Mg-substituted crystalline calcite
journal, December 2010
- Elstnerová, Pavlína; Friák, Martin; Fabritius, Helge Otto
- Acta Biomaterialia, Vol. 6, Issue 12
Template-Dependent Morphogenesis of Oriented Calcite Crystals in the Presence of Magnesium Ions
journal, April 2005
- Han, Yong-Jin; Wysocki, Laura M.; Thanawala, Monica S.
- Angewandte Chemie International Edition, Vol. 44, Issue 16
Turning Down the Heat: Design and Mechanism in Solid-State Synthesis
journal, March 1993
- Stein, A.; Keller, S. W.; Mallouk, T. E.
- Science, Vol. 259, Issue 5101
New Estimates of the Free Energy of Calcite/Water Interfaces for Evaluating the Equilibrium Shape and Nucleation Mechanisms
journal, February 2013
- Bruno, Marco; Massaro, Francesco Roberto; Pastero, Linda
- Crystal Growth & Design, Vol. 13, Issue 3
Stable prenucleation mineral clusters are liquid-like ionic polymers
journal, September 2011
- Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.
- Nature Communications, Vol. 2, Issue 1
Control of crystal phase switching and orientation by soluble mollusc-shell proteins
journal, May 1996
- Belcher, A. M.; Wu, X. H.; Christensen, R. J.
- Nature, Vol. 381, Issue 6577
Keimbildungsgeschwindigkeit und OSTWALDsche Stufenregel
journal, January 1933
- Stranski, I. N.; Totomanow, D.
- Zeitschrift für Physikalische Chemie, Vol. 163A, Issue 1
Dissolution Enthalpies of Magnesian Calcites
journal, September 1998
- Bischoff, William D.
- Aquatic Geochemistry, Vol. 4, Issue 3/4, p. 321-336
The solubility of calcite in seawater solutions of various magnesium concentration, at 25 °C and one atmosphere total pressure
journal, April 1984
- Mucci, Alfonso; Morse, John W.
- Geochimica et Cosmochimica Acta, Vol. 48, Issue 4
Efficient creation and convergence of surface slabs
journal, November 2013
- Sun, Wenhao; Ceder, Gerbrand
- Surface Science, Vol. 617
Reconstructing Past Seawater Mg/Ca and Sr/Ca from Mid-Ocean Ridge Flank Calcium Carbonate Veins
journal, February 2010
- Coggon, R. M.; Teagle, D. A. H.; Smith-Duque, C. E.
- Science, Vol. 327, Issue 5969
Limit of validity of Ostwald's rule of stages in a statistical mechanical model of crystallization
journal, October 2011
- Hedges, Lester O.; Whitelam, Stephen
- The Journal of Chemical Physics, Vol. 135, Issue 16
Nucleation and growth of magnetite from solution
journal, February 2013
- Baumgartner, Jens; Dey, Archan; Bomans, Paul H. H.
- Nature Materials, Vol. 12, Issue 4
Chimie Douce Approaches to the Synthesis of Metastable Oxide Materials
journal, July 1995
- Gopalakrishnan, J.
- Chemistry of Materials, Vol. 7, Issue 7
Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate
journal, September 2010
- Radha, A. V.; Forbes, T. Z.; Killian, C. E.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 38
Energetic clues to pathways to biomineralization: Precursors, clusters, and nanoparticles
journal, August 2004
- Navrotsky, A.
- Proceedings of the National Academy of Sciences, Vol. 101, Issue 33
Thermodynamics of Carbonates
journal, January 2013
- Radha, A. V.; Navrotsky, A.
- Reviews in Mineralogy and Geochemistry, Vol. 77, Issue 1
Ostwald’s Rule of Stages and Its Role in CdSe Quantum Dot Crystallization
journal, October 2012
- Washington, Aaron L.; Foley, Megan E.; Cheong, Soshan
- Journal of the American Chemical Society, Vol. 134, Issue 41
Calcium Carbonate Formation and Dissolution
journal, February 2007
- Morse, John W.; Arvidson, Rolf S.; Lüttge, Andreas
- Chemical Reviews, Vol. 107, Issue 2
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Influences of temperature and Mg:Ca ratio on CaCO3 precipitates from seawater
journal, January 1997
- Morse, John W.; Wang, Qiwei; Tsio, Mai Yin
- Geology, Vol. 25, Issue 1
Stable Prenucleation Calcium Carbonate Clusters
journal, December 2008
- Gebauer, Denis; Völkel, Antje; Cölfen, Helmut
- Science, Vol. 322, Issue 5909
Testing the cation-hydration effect on the crystallization of Ca-Mg-CO3 systems
journal, October 2013
- Xu, J.; Yan, C.; Zhang, F.
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 44
The role of magnesium in the crystal growth of calcite and aragonite from sea water
journal, April 1975
- Berner, R. A.
- Geochimica et Cosmochimica Acta, Vol. 39, Issue 4, p. 489-504
Activity–composition relations in the system CaCO3–MgCO3 predicted from static structure energy calculations and Monte Carlo simulations
journal, February 2007
- Vinograd, Victor L.; Burton, Benjamin P.; Gale, Julian D.
- Geochimica et Cosmochimica Acta, Vol. 71, Issue 4
Mixed calcium-magnesium pre-nucleation clusters enrich calcium
journal, November 2012
- Verch, Andreas; Antonietti, Markus; Cölfen, Helmut
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 227, Issue 11
Calcite and Aragonite Precipitation Under Controlled Instantaneous Supersaturation: Elucidating the Role of CaCO3 Saturation State and Mg/Ca Ratio on Calcium Carbonate Polymorphism
journal, June 2009
- De Choudens-Sanchez, V.; Gonzalez, L. A.
- Journal of Sedimentary Research, Vol. 79, Issue 6
Nanoscale Effects on Thermodynamics and Phase Equilibria in Oxide Systems
journal, July 2011
- Navrotsky, Alexandra
- ChemPhysChem, Vol. 12, Issue 12
Ostwald processes and mineral paragenesis in sediments
journal, June 1988
- Morse, J. W.; Casey, W. H.
- American Journal of Science, Vol. 288, Issue 6
Mechanistic Insights into the Crystallization of Amorphous Calcium Carbonate (ACC)
journal, May 2012
- Bots, Pieter; Benning, Liane G.; Rodriguez-Blanco, Juan-Diego
- Crystal Growth & Design, Vol. 12, Issue 7
Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms
journal, September 2005
- Orr, James C.; Fabry, Victoria J.; Aumont, Olivier
- Nature, Vol. 437, Issue 7059
Significance of controlling crystallization mechanisms and kinetics in pharmaceutical systems
journal, July 1999
- Rodríguez‐hornedo, Naír; Murphy, Denette
- Journal of Pharmaceutical Sciences, Vol. 88, Issue 7
The Role of Mg2+ as an Impurity in Calcite Growth
journal, November 2000
- Davis, K. J.
- Science, Vol. 290, Issue 5494
Studien über die Bildung und Umwandlung fester Körper
journal, January 1897
- Ostwald, W.
- Zeitschrift für Physikalische Chemie, Vol. 22U, Issue 1
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013
- Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav
- Computational Materials Science, Vol. 68