Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution

Zhu, Yaguang; Li, Qingyun; Kim, Doyoon; Min, Yujia; Lee, Byeongdu; Jun, Young-Shin

doi:10.1021/acs.est.1c02865

Sulfate-Controlled Heterogeneous CaCO₃ Nucleation and Its Non-linear Interfacial Energy Evolution

Journal Article · Tue Jul 27 00:00:00 EDT 2021 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.1c02865· OSTI ID:1840567

^[1]; ^[1]; ^[1]; ^[1]; Lee, Byeongdu ^[2]; ^[1]

Washington Univ., St. Louis, MO (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Unveiling the effects of an environmental abundant anion “sulfate” on the formation of calcium carbonate (CaCO₃) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate–CaCO₃ interactions at the explicit first step of CaCO₃ formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO₃ nucleation is monitored in real time as a function of sulfate concentrations (0–10 mM Na₂SO₄) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO₃ nucleation rate, causing a 120% increase in the CaCO₃ nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO₃ and finds a non-linear trend, suggesting that CaCO₃ heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO₃ interfacial energies, a key step toward achieving natural and engineered controls on CaCO₃ nucleation.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Organization:: Energy Frontier Research Center

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1840567

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 16 Vol. 55; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization Addadi, L.; Raz, S.; Weiner, S. Advanced Materials, Vol. 15, Issue 12 https://doi.org/10.1002/adma.200300381	journal	June 2003
Nanoscale Effects on Thermodynamics and Phase Equilibria in Oxide Systems Navrotsky, Alexandra ChemPhysChem, Vol. 12, Issue 12 https://doi.org/10.1002/cphc.201100129	journal	July 2011
The solubility of calcite in seawater solutions of various magnesium concentration, at 25 °C and one atmosphere total pressure Mucci, Alfonso; Morse, John W. Geochimica et Cosmochimica Acta, Vol. 48, Issue 4 https://doi.org/10.1016/0016-7037(84)90103-0	journal	April 1984
A new kinetic approach to modeling water-rock interaction: The role of nucleation, precursors, and Ostwald ripening Steefel, Carl I.; Van Cappellen, Philippe Geochimica et Cosmochimica Acta, Vol. 54, Issue 10 https://doi.org/10.1016/0016-7037(90)90003-4	journal	October 1990
Petroleum, oil field waters, and authigenic mineral assemblages Are they in metastable equilibrium in hydrocarbon reservoirs Helgeson, Harold C.; Knox, Annette M.; Owens, Christine E. Geochimica et Cosmochimica Acta, Vol. 57, Issue 14 https://doi.org/10.1016/0016-7037(93)90541-4	journal	July 1993
The crystallization of calcium carbonate Reddy, M. M.; Nancollas, G. H. Journal of Crystal Growth, Vol. 35, Issue 1 https://doi.org/10.1016/0022-0248(76)90240-2	journal	August 1976
Correction for solute/solvent interaction extends accurate freezing point depression theory to high concentration range Fullerton, Gary D.; Keener, Carl R.; Cameron, Ivan L. Journal of Biochemical and Biophysical Methods, Vol. 29, Issue 3-4 https://doi.org/10.1016/0165-022X(94)90034-5	journal	December 1994
Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa Cusack, Maggie; Dauphin, Yannicke; Cuif, Jean-Pierre Chemical Geology, Vol. 253, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2008.05.007	journal	August 2008
The role of sulfate groups in controlling CaCO₃ polymorphism Fernández-Díaz, Lurdes; Fernández-González, Ángeles; Prieto, Manuel Geochimica et Cosmochimica Acta, Vol. 74, Issue 21, p. 6064-6076 https://doi.org/10.1016/j.gca.2010.08.010	journal	November 2010
Crystallization of CaCO₃ in the presence of sulfate and additives: Experimental and molecular dynamics simulation studies Tang, Yongming; Zhang, Fan; Cao, Ziyi Journal of Colloid and Interface Science, Vol. 377, Issue 1, p. 430-437 https://doi.org/10.1016/j.jcis.2012.02.069	journal	July 2012
A study of CaCO3 scale formation and inhibition in RO and NF membrane processes Tzotzi, C.; Pahiadaki, T.; Yiantsios, S. Journal of Membrane Science, Vol. 296, Issue 1-2 https://doi.org/10.1016/j.memsci.2007.03.031	journal	June 2007
Heterogeneous Nucleation and Growth of Nanoparticles at Environmental Interfaces Jun, Young-Shin; Kim, Doyoon; Neil, Chelsea W. Accounts of Chemical Research, Vol. 49, Issue 9 https://doi.org/10.1021/acs.accounts.6b00208	journal	August 2016
Surface Wetting Controls Calcium Carbonate Crystallization Kinetics Koishi, Ayumi; Fernandez-Martinez, Alejandro; Van Driessche, Alexander E. S. Chemistry of Materials, Vol. 31, Issue 9 https://doi.org/10.1021/acs.chemmater.9b00417	journal	April 2019
Ionic Strength-Controlled Mn (Hydr)oxide Nanoparticle Nucleation on Quartz: Effect of Aqueous Mn(OH) ₂ Jung, Haesung; Jun, Young-Shin Environmental Science & Technology, Vol. 50, Issue 1 https://doi.org/10.1021/acs.est.5b02819	journal	December 2015
Incorporating Nanoscale Effects into a Continuum-Scale Reactive Transport Model for CO ₂ -Deteriorated Cement Li, Qingyun; Steefel, Carl I.; Jun, Young-Shin Environmental Science & Technology, Vol. 51, Issue 18 https://doi.org/10.1021/acs.est.7b00594	journal	September 2017
Wollastonite Carbonation in Water-Bearing Supercritical CO ₂ : Effects of Particle Size Min, Yujia; Li, Qingyun; Voltolini, Marco Environmental Science & Technology, Vol. 51, Issue 21 https://doi.org/10.1021/acs.est.7b04475	journal	October 2017
Salinity-Induced Reduction of Interfacial Energies and Kinetic Factors during Calcium Carbonate Nucleation on Quartz Li, Qingyun; Jun, Young-Shin The Journal of Physical Chemistry C, Vol. 123, Issue 23 https://doi.org/10.1021/acs.jpcc.9b00378	journal	May 2019
Structural Match of Heterogeneously Nucleated Mn(OH) ₂ (s) Nanoparticles on Quartz under Various pH Conditions Jung, Haesung; Lee, Byeongdu; Jun, Young-Shin Langmuir, Vol. 32, Issue 41 https://doi.org/10.1021/acs.langmuir.6b02446	journal	October 2016
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
Calcium Carbonate Formation and Dissolution Morse, John W.; Arvidson, Rolf S.; Lüttge, Andreas Chemical Reviews, Vol. 107, Issue 2 https://doi.org/10.1021/cr050358j	journal	February 2007
In Situ Observations of Nanoparticle Early Development Kinetics at Mineral−Water Interfaces Jun, Young-Shin; Lee, Byeongdu; Waychunas, Glenn A. Environmental Science & Technology, Vol. 44, Issue 21 https://doi.org/10.1021/es101491e	journal	November 2010
In Situ Determination of Interfacial Energies between Heterogeneously Nucleated CaCO ₃ and Quartz Substrates: Thermodynamics of CO ₂ Mineral Trapping Fernandez-Martinez, Alejandro; Hu, Yandi; Lee, Byeongdu Environmental Science & Technology, Vol. 47, Issue 1 https://doi.org/10.1021/es3014826	journal	June 2012
Control of Heterogeneous Fe(III) (Hydr)oxide Nucleation and Growth by Interfacial Energies and Local Saturations Hu, Yandi; Neil, Chelsea; Lee, Byeongdu Environmental Science & Technology, Vol. 47, Issue 16 https://doi.org/10.1021/es401160g	journal	August 2013
Aluminum Affects Heterogeneous Fe(III) (Hydr)oxide Nucleation, Growth, and Ostwald Ripening Hu, Yandi; Li, Qingyun; Lee, Byeongdu Environmental Science & Technology, Vol. 48, Issue 1 https://doi.org/10.1021/es403777w	journal	December 2013
Interfacial Energies for Heterogeneous Nucleation of Calcium Carbonate on Mica and Quartz Li, Qingyun; Fernandez-Martinez, Alejandro; Lee, Byeongdu Environmental Science & Technology, Vol. 48, Issue 10 https://doi.org/10.1021/es405141j	journal	May 2014
Different Arsenate and Phosphate Incorporation Effects on the Nucleation and Growth of Iron(III) (Hydr)oxides on Quartz Neil, Chelsea W.; Lee, Byeongdu; Jun, Young-Shin Environmental Science & Technology, Vol. 48, Issue 20 https://doi.org/10.1021/es503251z	journal	October 2014
Effects of Sulfate during CO ₂ Attack on Portland Cement and Their Impacts on Mechanical Properties under Geologic CO ₂ Sequestration Conditions Li, Qingyun; Lim, Yun Mook; Jun, Young-Shin Environmental Science & Technology, Vol. 49, Issue 11 https://doi.org/10.1021/es506349u	journal	May 2015
Environmentally Abundant Anions Influence the Nucleation, Growth, Ostwald Ripening, and Aggregation of Hydrous Fe(III) Oxides Hu, Yandi; Lee, Byeongdu; Bell, Christopher Langmuir, Vol. 28, Issue 20 https://doi.org/10.1021/la300791w	journal	May 2012
Molecular recognition in biomineralization Mann, Stephen Nature, Vol. 332, Issue 6160 https://doi.org/10.1038/332119a0	journal	March 1988
Formation of calcium sulfate through the aggregation of sub-3 nanometre primary species Stawski, Tomasz M.; van Driessche, Alexander E. S.; Ossorio, Mercedes Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11177	journal	April 2016
Stable prenucleation mineral clusters are liquid-like ionic polymers Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D. Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1604	journal	September 2011
Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate Habraken, Wouter J. E. M.; Tao, Jinhui; Brylka, Laura J. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2490	journal	February 2013
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
Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy Smeets, Paul J. M.; Cho, Kang Rae; Kempen, Ralph G. E. Nature Materials, Vol. 14, Issue 4 https://doi.org/10.1038/nmat4193	journal	January 2015
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
Antiscaling efficacy of CaCO ₃ and CaSO ₄ on polyethylene glycol (PEG)-modified reverse osmosis membranes in the presence of humic acid: interplay of membrane surface properties and water chemistry Ray, Jessica R.; Wong, Whitney; Jun, Young-Shin Physical Chemistry Chemical Physics, Vol. 19, Issue 7 https://doi.org/10.1039/C6CP08569E	journal	January 2017
Thermodynamics of solvation of ions. Part 5.—Gibbs free energy of hydration at 298.15 K Marcus, Yizhak J. Chem. Soc., Faraday Trans., Vol. 87, Issue 18 https://doi.org/10.1039/FT9918702995	journal	January 1991
Energetic clues to pathways to biomineralization: Precursors, clusters, and nanoparticles Navrotsky, A. Proceedings of the National Academy of Sciences, Vol. 101, Issue 33 https://doi.org/10.1073/pnas.0404778101	journal	August 2004
Animal evolution, bioturbation, and the sulfate concentration of the oceans Canfield, D. E.; Farquhar, J. Proceedings of the National Academy of Sciences, Vol. 106, Issue 20 https://doi.org/10.1073/pnas.0902037106	journal	May 2009
Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate Radha, A. V.; Forbes, T. Z.; Killian, C. E. Proceedings of the National Academy of Sciences, Vol. 107, Issue 38 https://doi.org/10.1073/pnas.1009959107	journal	September 2010
Polysaccharide chemistry regulates kinetics of calcite nucleation through competition of interfacial energies Giuffre, Anthony J.; Hamm, Laura M.; Han, Nizhou Proceedings of the National Academy of Sciences, Vol. 110, Issue 23 https://doi.org/10.1073/pnas.1222162110	journal	May 2013
Nucleation of metastable aragonite CaCO ₃ in seawater Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei Proceedings of the National Academy of Sciences, Vol. 112, Issue 11 https://doi.org/10.1073/pnas.1423898112	journal	March 2015
Refinement of the atomic parameters of α-quartz Smith, G. S.; Alexander, L. E. Acta Crystallographica, Vol. 16, Issue 6 https://doi.org/10.1107/S0365110X63001298	journal	June 1963
Impact of Anthropogenic CO2 on the CaCO3 System in the Oceans Feely, R. A. Science, Vol. 305, Issue 5682 https://doi.org/10.1126/science.1097329	journal	July 2004
Sea Urchin Spine Calcite Forms via a Transient Amorphous Calcium Carbonate Phase Politi, Y. Science, Vol. 306, Issue 5699 https://doi.org/10.1126/science.1102289	journal	November 2004
Stable Prenucleation Calcium Carbonate Clusters Gebauer, Denis; Völkel, Antje; Cölfen, Helmut Science, Vol. 322, Issue 5909 https://doi.org/10.1126/science.1164271	journal	December 2008
The Initial Stages of Template-Controlled CaCO₃ Formation Revealed by Cryo-TEM Pouget, E. M.; Bomans, P. H. H.; Goos, J. A. C. M. Science, Vol. 323, Issue 5920, p. 1455-1458 https://doi.org/10.1126/science.1169434	journal	March 2009
In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways Nielsen, M. H.; Aloni, S.; De Yoreo, J. J. Science, Vol. 345, Issue 6201 https://doi.org/10.1126/science.1254051	journal	September 2014
Aragonite-calcite seas—Quantifying the gray area Balthasar, Uwe; Cusack, Maggie Geology, Vol. 43, Issue 2 https://doi.org/10.1130/G36293.1	journal	February 2015
Dolomitization kinetics of hydrothermal bombs and natural settings Sibley, D. F.; Nordeng, S. H.; Borkowski, M. L. Journal of Sedimentary Research, Vol. 64, Issue 3a https://doi.org/10.1306/D4267E29-2B26-11D7-8648000102C1865D	journal	July 1994
Structure of vaterite and infrared spectra Sato, Mitsuo; Matsuda, Shunji Zeitschrift für Kristallographie, Vol. 129, Issue 5-6 https://doi.org/10.1524/zkri.1969.129.5-6.405	journal	August 1969
Principles of Crystal Nucleation and Growth De Yoreo, J. J. Reviews in Mineralogy and Geochemistry, Vol. 54, Issue 1 https://doi.org/10.2113/0540057	journal	January 2003
Thermal expansion of gypsum investigated by neutron powder diffraction Schofield, Paul F.; Knight, Kevin S.; Stretton, Iona C. American Mineralogist, Vol. 81, Issue 7-8 https://doi.org/10.2138/am-1996-7-807	journal	August 1996
Structure and carbonate orientation of vaterite (CaCO3) Wang, J.; Becker, U. American Mineralogist, Vol. 94, Issue 2-3 https://doi.org/10.2138/am.2009.2939	journal	February 2009
Infrared Spectra of Amorphous and Crystalline Calcium Carbonate. Andersen, Flemming A.; Brečević, Ljerka; Beuter, Georg Acta Chemica Scandinavica, Vol. 45 https://doi.org/10.3891/acta.chem.scand.45-1018	journal	January 1991

Similar Records

Process-Specific Effects of Sulfate on CaCO₃ Formation in Environmentally Relevant Systems

Journal Article · Wed May 25 20:00:00 EDT 2022 · Environmental Science and Technology · OSTI ID:1962067

In Situ Determination of Interfacial Energies between Heterogeneously Nucleated CaCO ₃ and Quartz Substrates: Thermodynamics of CO ₂ Mineral Trapping

Journal Article · Tue Jan 01 23:00:00 EST 2013 · Environmental Science and Technology · OSTI ID:1080659

Salinity-Induced Reduction of Interfacial Energies and Kinetic Factors during Calcium Carbonate Nucleation on Quartz

Journal Article · Mon May 13 20:00:00 EDT 2019 · Journal of Physical Chemistry. C · OSTI ID:1547040

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CaCO3
calcite
heterogeneous nucleation
interfacial energy
sulfate
vaterite

Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution

Citation Formats

References (55)

Similar Records

Related Subjects

Sulfate-Controlled Heterogeneous CaCO₃ Nucleation and Its Non-linear Interfacial Energy Evolution