Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO3 Mechanism Controversy

Chen, Si Athena; Weber, Juliane; Starchenko, Vitalii; Eng, Peter J.; Stubbs, Joanne E.; Wang, Hsiu-Wen; Liu, Tingting; Spano, Tyler L.; Chakoumakos, Bryan C.; Stack, Andrew G.

doi:10.1021/acs.cgd.4c00245

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO₃ Mechanism Controversy

Journal Article · Wed May 22 00:00:00 EDT 2024 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.4c00245· OSTI ID:2371072

^[1]; ^[1]; ^[1]; ^[2]; ^[2]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of Chicago, IL (United States)

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO₃), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s^–1] and solid-state transformation at 280 °C [0.00134(11) s^–1]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725; SC0019108

OSTI ID:: 2371072

Journal Information:: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 12 Vol. 24; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Assessing ocean alkalinity for carbon sequestration: Ocean Alkalinity for C Sequestration Renforth, Phil; Henderson, Gideon Reviews of Geophysics, Vol. 55, Issue 3 https://doi.org/10.1002/2016RG000533	journal	July 2017
Amorphous Calcium Carbonate is Stabilized in Confinement Stephens, Christopher J.; Ladden, Sophie F.; Meldrum, Fiona C. Advanced Functional Materials, Vol. 20, Issue 13 https://doi.org/10.1002/adfm.201000248	journal	June 2010
Particle Accretion Mechanism Underlies Biological Crystal Growth from an Amorphous Precursor Phase Gal, Assaf; Kahil, Keren; Vidavsky, Netta Advanced Functional Materials, Vol. 24, Issue 34 https://doi.org/10.1002/adfm.201400676	journal	July 2014
Crystallization in Patterns: A Bio-Inspired Approach Aizenberg, J. Advanced Materials, Vol. 16, Issue 15 https://doi.org/10.1002/adma.200400759	journal	August 2004
Calcite Crystal Growth by a Solid-State Transformation of Stabilized Amorphous Calcium Carbonate Nanospheres in a Hydrogel Gal, Assaf; Habraken, Wouter; Gur, Dvir Angewandte Chemie International Edition, Vol. 52, Issue 18 https://doi.org/10.1002/anie.201210329	journal	April 2013
Solid-State Transformation of Amorphous Calcium Carbonate to Aragonite Captured by CryoTEM Walker, Jessica M.; Marzec, Bartosz; Nudelman, Fabio Angewandte Chemie International Edition, Vol. 56, Issue 39 https://doi.org/10.1002/anie.201703158	journal	August 2017
Use of Amorphous Calcium Carbonate for the Design of New Materials Cantaert, Bram; Kuo, David; Matsumura, Shunichi ChemPlusChem, Vol. 82, Issue 1 https://doi.org/10.1002/cplu.201600457	journal	November 2016
Mollusc larval shell formation: amorphous calcium carbonate is a precursor phase for aragonite Weiss, Ingrid Maria; Tuross, Noreen; Addadi, Lia Journal of Experimental Zoology, Vol. 293, Issue 5 https://doi.org/10.1002/jez.90004	journal	August 2002
Amorphous, nanocrystalline and crystalline calcium carbonates in biological materials Wehrmeister, U.; Jacob, D. E.; Soldati, A. L. Journal of Raman Spectroscopy, Vol. 42, Issue 5 https://doi.org/10.1002/jrs.2835	journal	November 2010
Neutron powder diffraction study of the orientational order–disorder phase transition in calcite, CaCO3 Dove, Martin T.; Swainson, Ian P.; Powell, Brian M. Physics and Chemistry of Minerals, Vol. 32, Issue 7 https://doi.org/10.1007/s00269-005-0026-1	journal	September 2005
The rate and mechanism of polymorphic transformation of calcium carbonate in water Ogino, Takeshi; Suzuki, Toshio; Sawada, Kiyoshi Journal of Crystal Growth, Vol. 100, Issue 1-2 https://doi.org/10.1016/0022-0248(90)90618-U	journal	February 1990
Variation in calcite dissolution rates: Arvidson, Rolf S.; Ertan, Inci Evren; Amonette, James E. Geochimica et Cosmochimica Acta, Vol. 67, Issue 9 https://doi.org/10.1016/S0016-7037(02)01177-8	journal	May 2003
Carbonate minerals in the global carbon cycle Martin, Jonathan B. Chemical Geology, Vol. 449 https://doi.org/10.1016/j.chemgeo.2016.11.029	journal	January 2017
Hematite-goethite ratios at pH 2–13 and 25–170 °C: A time-resolved synchrotron X-ray diffraction study Chen, Si Athena; Heaney, Peter J.; Post, Jeffrey E. Chemical Geology, Vol. 606 https://doi.org/10.1016/j.chemgeo.2022.120995	journal	September 2022
State of art of natural inhibitors of calcium carbonate scaling. A review article Chaussemier, Marie; Pourmohtasham, Ermane; Gelus, Dominique Desalination, Vol. 356 https://doi.org/10.1016/j.desal.2014.10.014	journal	January 2015
Origin of a global carbonate layer deposited in the aftermath of the Cretaceous-Paleogene boundary impact Bralower, Timothy J.; Cosmidis, Julie; Heaney, Peter J. Earth and Planetary Science Letters, Vol. 548 https://doi.org/10.1016/j.epsl.2020.116476	journal	October 2020
Monohydrocalcite in calcareous corpuscles of Mesocestoides corti Señorale-Pose, Mario; Chalar, Cora; Dauphin, Yannicke Experimental Parasitology, Vol. 118, Issue 1 https://doi.org/10.1016/j.exppara.2007.06.011	journal	January 2008
Nanoscale effects of strontium on calcite growth: An in situ AFM study in the absence of vital effects Wasylenki, Laura E.; Dove, Patricia M.; Wilson, Darren S. Geochimica et Cosmochimica Acta, Vol. 69, Issue 12 https://doi.org/10.1016/j.gca.2004.12.019	journal	June 2005
Isotopic tracer evidence for the amorphous calcium carbonate to calcite transformation by dissolution–reprecipitation Giuffre, Anthony J.; Gagnon, Alexander C.; De Yoreo, James J. Geochimica et Cosmochimica Acta, Vol. 165 https://doi.org/10.1016/j.gca.2015.06.002	journal	September 2015
Chemical and physical controls on the transformation of amorphous calcium carbonate into crystalline CaCO3 polymorphs Blue, C. R.; Giuffre, A.; Mergelsberg, S. Geochimica et Cosmochimica Acta, Vol. 196 https://doi.org/10.1016/j.gca.2016.09.004	journal	January 2017
Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D) Cao, Bo; Stack, Andrew G.; Steefel, Carl I. Geochimica et Cosmochimica Acta, Vol. 222 https://doi.org/10.1016/j.gca.2017.10.020	journal	February 2018
The role of pH and Mg on the stability and crystallization of amorphous calcium carbonate Rodriguez-Blanco, J. D.; Shaw, S.; Bots, P. Journal of Alloys and Compounds, Vol. 536 https://doi.org/10.1016/j.jallcom.2011.11.057	journal	September 2012
Amorphous calcium carbonate associated with biofilms in hot spring deposits Jones, Brian; Peng, Xiaotong Sedimentary Geology, Vol. 269-270 https://doi.org/10.1016/j.sedgeo.2012.05.019	journal	August 2012
Evolution in the structure of akaganeite and hematite during hydrothermal growth: an in situ synchrotron X-ray diffraction analysis Peterson, Kristina M.; Heaney, Peter J.; Post, Jeffrey E. Powder Diffraction, Vol. 33, Issue 4 https://doi.org/10.1017/S0885715618000623	journal	September 2018
Ab Initio Molecular Dynamics Simulations of Amorphous Calcium Carbonate: Interpretation of Pair Distribution Function and X-ray Absorption Spectroscopy Data Prange, Micah P.; Mergelsberg, Sebastian T.; Kerisit, Sebastien N. Crystal Growth & Design, Vol. 21, Issue 4 https://doi.org/10.1021/acs.cgd.0c01655	journal	March 2021
Opposing Effects of Impurity Ion Sr ²⁺ on the Heterogeneous Nucleation and Growth of Barite (BaSO ₄ ) Yuan, Ke; Starchenko, Vitalii; Rampal, Nikhil Crystal Growth & Design, Vol. 21, Issue 10 https://doi.org/10.1021/acs.cgd.1c00715	journal	September 2021
Mechanism of Enhanced Strontium Uptake into Calcite via an Amorphous Calcium Carbonate Crystallization Pathway Littlewood, Janice L.; Shaw, Samuel; Peacock, Caroline L. Crystal Growth & Design, Vol. 17, Issue 3 https://doi.org/10.1021/acs.cgd.6b01599	journal	January 2017
Reaction Pathway of the Hydrothermal Synthesis of AgCuO₂ from In Situ Time-Resolved X-ray Diffraction Liu, Hongjun; Grendal, Ola G.; Skjærvø, Susanne Linn Crystal Growth & Design, Vol. 20, Issue 7 https://doi.org/10.1021/acs.cgd.9b01516	journal	April 2020
Opposite Particle Size Effect on Amorphous Calcium Carbonate Crystallization in Water and during Heating in Air Zou, Zhaoyong; Bertinetti, Luca; Politi, Yael Chemistry of Materials, Vol. 27, Issue 12 https://doi.org/10.1021/acs.chemmater.5b00145	journal	June 2015
Numerical Study of Mineral Nucleation and Growth on a Substrate Yang, Fengchang; Yuan, Ke; Stack, Andrew G. ACS Earth and Space Chemistry, Vol. 6, Issue 7 https://doi.org/10.1021/acsearthspacechem.1c00376	journal	June 2022
Mapping Three-dimensional Dissolution Rates of Calcite Microcrystals: Effects of Surface Curvature and Dissolved Metal Ions Yuan, Ke; Starchenko, Vitalii; Lee, Sang Soo ACS Earth and Space Chemistry, Vol. 3, Issue 5 https://doi.org/10.1021/acsearthspacechem.9b00003	journal	February 2019
Calcite Growth Rates As a Function of Aqueous Calcium-to-Carbonate Ratio, Saturation Index, and Inhibitor Concentration: Insight into the Mechanism of Reaction and Poisoning by Strontium Bracco, Jacquelyn N.; Grantham, Meg C.; Stack, Andrew G. Crystal Growth & Design, Vol. 12, Issue 7 https://doi.org/10.1021/cg300350k	journal	June 2012
Mechanistic Insights into the Crystallization of Amorphous Calcium Carbonate (ACC) Bots, Pieter; Benning, Liane G.; Rodriguez-Blanco, Juan-Diego Crystal Growth & Design, Vol. 12, Issue 7 https://doi.org/10.1021/cg300676b	journal	May 2012
Structural Changes upon Dehydration of Amorphous Calcium Carbonate Schmidt, Millicent P.; Ilott, Andrew J.; Phillips, Brian L. Crystal Growth & Design, Vol. 14, Issue 3 https://doi.org/10.1021/cg401073n	journal	January 2014
Structural Characteristics of Synthetic Amorphous Calcium Carbonate Michel, F. Marc; MacDonald, Jason; Feng, Jian Chemistry of Materials, Vol. 20, Issue 14 https://doi.org/10.1021/cm800324v	journal	July 2008
Crystal growth of calcium carbonate. A controlled composition kinetic study Kazmierczak, T. F.; Tomson, M. B.; Nancollas, G. H. The Journal of Physical Chemistry, Vol. 86, Issue 1 https://doi.org/10.1021/j100390a020	journal	January 1982
Hydration of the Calcium Ion. An EXAFS, Large-Angle X-ray Scattering, and Molecular Dynamics Simulation Study Jalilehvand, Farideh; Spångberg, Daniel; Lindqvist-Reis, Patric Journal of the American Chemical Society, Vol. 123, Issue 3 https://doi.org/10.1021/ja001533a	journal	January 2001
Dehydration and crystallization of amorphous calcium carbonate in solution and in air Ihli, Johannes; Wong, Wai Ching; Noel, Elizabeth H. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4169	journal	January 2014
The apparent activation energy and pre-exponential kinetic factor for heterogeneous calcium carbonate nucleation on quartz Li, Qingyun; Jun, Young-Shin Communications Chemistry, Vol. 1, Issue 1 https://doi.org/10.1038/s42004-018-0056-5	journal	September 2018
The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, viavaterite. Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G. Nanoscale, Vol. 3, Issue 1 https://doi.org/10.1039/C0NR00589D	journal	January 2011
Controlling nucleation in giant liposomes Tester, Chantel C.; Whittaker, Michael L.; Joester, Derk Chem. Commun., Vol. 50, Issue 42 https://doi.org/10.1039/C4CC01457J	journal	January 2014
Formation of amorphous calcium carbonate and its transformation into mesostructured calcite Rodriguez-Navarro, Carlos; Kudłacz, Krzysztof; Cizer, Özlem CrystEngComm, Vol. 17, Issue 1 https://doi.org/10.1039/C4CE01562B	journal	January 2015
Synthesis and structure of synthetically pure and deuterated amorphous (basic) calcium carbonates Wang, Hsiu-Wen; Daemen, Luke L.; Cheshire, Michael C. Chemical Communications, Vol. 53, Issue 20 https://doi.org/10.1039/C6CC08848A	journal	January 2017
Nanopore facilitated monohydrocalcitic amorphous calcium carbonate precipitation Page, Katharine; Stack, Andrew G.; Chen, Si Athena Physical Chemistry Chemical Physics, Vol. 24, Issue 30 https://doi.org/10.1039/D2CP00446A	journal	January 2022
Kinetics of Phase Change. I General Theory Avrami, Melvin The Journal of Chemical Physics, Vol. 7, Issue 12, p. 1103-1112 https://doi.org/10.1063/1.1750380	journal	December 1939
Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule Politi, Y.; Metzler, R. A.; Abrecht, M. Proceedings of the National Academy of Sciences, Vol. 105, Issue 45 https://doi.org/10.1073/pnas.0806604105	journal	November 2008
Amorphous calcium carbonate particles form coral skeletons Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu Proceedings of the National Academy of Sciences, Vol. 114, Issue 37 https://doi.org/10.1073/pnas.1707890114	journal	August 2017
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
Minerals formed by organisms Lowenstam, H. Science, Vol. 211, Issue 4487 https://doi.org/10.1126/science.7008198	journal	March 1981
Crystallization by particle attachment in synthetic, biogenic, and geologic environments De Yoreo, J. J.; Gilbert, P. U. P. A.; Sommerdijk, N. A. J. M. Science, Vol. 349, Issue 6247 https://doi.org/10.1126/science.aaa6760	journal	July 2015
Superhydrous hematite and goethite: A potential water reservoir in the red dust of Mars? Chen, Si Athena; Heaney, Peter J.; Post, Jeffrey E. Geology, Vol. 49, Issue 11 https://doi.org/10.1130/g48929.1	journal	July 2021
The non-classical nucleation of crystals: microscopic mechanisms and applications to molecular crystals, ice and calcium carbonate Sear, R. P. International Materials Reviews, Vol. 57, Issue 6 https://doi.org/10.1179/1743280411Y.0000000015	journal	November 2012
Structural analyses of amorphous calcium carbonate before and after removing strontium ions from an aqueous solution Shuseki, Yuta; Kohara, Shinji; Ohara, Koji Journal of the Ceramic Society of Japan, Vol. 130, Issue 2 https://doi.org/10.2109/jcersj2.21155	journal	February 2022
A structural study of size-dependent lattice variation: In situ X-ray diffraction of the growth of goethite nanoparticles from 2-line ferrihydrite Heaney, Peter J.; Oxman, Matthew J.; Chen, Si Athena American Mineralogist, Vol. 105, Issue 5 https://doi.org/10.2138/am-2020-7217	journal	May 2020
Vacancy infilling during the crystallization of Fe-deficient hematite: An in situ synchrotron X-ray diffraction study of non-classical crystal growth Chen, Si Athena; Heaney, Peter J.; Post, Jeffrey E. American Mineralogist, Vol. 108, Issue 9 https://doi.org/10.2138/am-2022-8379	journal	September 2023
Continuous time-resolved X-ray diffraction of the biocatalyzed reduction of Mn oxide Fischer, T. B.; Heaney, P. J.; Jang, J. -H. American Mineralogist, Vol. 93, Issue 11-12 https://doi.org/10.2138/am.2008.3038	journal	November 2008
Pore-Scale Modeling of Mineral Growth and Nucleation in Reactive Flow Starchenko, Vitalii Frontiers in Water, Vol. 3 https://doi.org/10.3389/frwa.2021.800944	journal	January 2022
Facile Low Temperature Hydrothermal Synthesis of BaTiO3 Nanoparticles Studied by In Situ X-ray Diffraction Grendal, Ola; Blichfeld, Anders; Skjærvø, Susanne Crystals, Vol. 8, Issue 6 https://doi.org/10.3390/cryst8060253	journal	June 2018
Incorporation of Incompatible Strontium and Barium Ions into Calcite (CaCO3) through Amorphous Calcium Carbonate Saito, Ayaka; Kagi, Hiroyuki; Marugata, Shiho Minerals, Vol. 10, Issue 3 https://doi.org/10.3390/min10030270	journal	March 2020

Similar Records

Calcium Carbonate Storage in Amorphous Form and Its Template-Induced Crystallization

Journal Article · Fri Aug 31 00:00:00 EDT 2007 · Chemistry of Materials · OSTI ID:928183

The formation and transformation mechanism of calcium carbonate in water

Journal Article · Thu Oct 01 00:00:00 EDT 1987 · Geochimica et Cosmochimica Acta; (USA) · OSTI ID:7000745

Transformation and Crystallization Energetics of Synthetic and Biogenic Amorphous Calcium Carbonate

Journal Article · Thu Dec 31 23:00:00 EST 2009 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1065525

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Activation energy
Calcite
Crystal structure
Crystallization
Impurities

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO3 Mechanism Controversy

Citation Formats

References (59)

Similar Records

Related Subjects

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO₃ Mechanism Controversy