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Title: 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 that the calcite nucleation barriermore » surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. The ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

Authors:
 [1];  [1];  [2];  [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Div.
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1235156
Alternate Identifier(s):
OSTI ID: 1221824; OSTI ID: 1221825
Grant/Contract Number:  
AC02-05CH11231; FG02-96ER45571; AC02-98CH10886; EDCBEE
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: 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 CaCO3 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 CaCO3 in seawater. United States. doi:10.1073/pnas.1423898112.
Sun, Wenhao, Jayaraman, Saivenkataraman, Chen, Wei, Persson, Kristin A., and Ceder, Gerbrand. Wed . "Nucleation of metastable aragonite CaCO3 in seawater". United States. doi:10.1073/pnas.1423898112.
@article{osti_1235156,
title = {Nucleation of metastable aragonite CaCO3 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. The 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1073/pnas.1423898112

Citation Metrics:
Cited by: 36 works
Citation information provided by
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