Stable Prenucleation Calcium Carbonate Clusters
Abstract
Calcium carbonate forms scales, geological deposits, biominerals, and ocean sediments. Huge amounts of carbon dioxide are retained as carbonate ions, and calcium ions represent a major contribution to water hardness. Despite its relevance, little is known about the precipitation mechanism of calcium carbonate, and specified complex crystal structures challenge the classical view on nucleation considering the formation of metastable ion clusters. We demonstrate that dissolved calcium carbonate in fact contains stable prenucleation ion clusters forming even in undersaturated solution. The cluster formation can be characterized by means of equilibrium thermodynamics, applying a multiple-binding model, which allows for structural preformation. Stable clusters are the relevant species in calcium carbonate nucleation. Such mechanisms may also be important for the crystallization of other minerals.
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A variety of precursor phases exist in the early stages of carbonate crystallization, including prenucleation clusters, metastable liquid-like precursors, mesocrystals and amorphous and nanophase precursors.
“Recent studies have shown that a variety of precursor phases exist in the early stages of carbonate crystallization, including prenucleation clusters, metastable liquid-like precursors, mesocrystals and amorphous and nanophase precursors [114-123].”
From Thermodynamic and Kinetic Studies of Dolomite Formation: A Review (2023) · cites this paper as [115]
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“8 However, this picture remains under active debate, and non-classical pathways involving the progressive assembly of dynamic oligomers 6,9–11 and a liquid–liquid phase transition 12,13 have been proposed.”
- Authors
- Gebauer, D., Völkel, A., & Cölfen, H.
- Affiliations
- Max Planck Institute of Colloids and Interfaces (DE)
- Max Planck Institute of Colloids and Interfaces, Research Campus Golm, Am Mühlenberg 1, D-14424 Potsdam, Germany.
- ORCID
- Gebauer, Denis
- Venue
- Science
- Published
- 2008-12-19
- Volume
- 322
- Issue
- 5909
- Pages
- 1819-1822
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W2140524010
- Cited by
- 1,673
- References
- 2
- Citations by year
- 2026: 91 · 2025: 108 · 2024: 119 · 2023: 96 · 2022: 128 · 2021: 127 · 2020: 96 · 2019: 94 · 2018: 85 · 2017: 84 · 2016: 118 · 2015: 110 · 2014: 94 · 2013: 98 · 2012: 75
- FWCI
- 21.39
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Science (publishedVersion)
- PubMed (publishedVersion)
- Max Planck Institute for Plasma Physics (submittedVersion)
- Max Planck Digital Library (submittedVersion)
- KOPS (University of Konstanz) (submittedVersion)
- MPG.PuRe (Max Planck Society) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
- Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
- Physical Sciences › Environmental Science › Environmental Engineering › Microbial Applications in Construction Materials
- Keywords
- calcium carbonate, prenucleation clusters, cluster ions, nucleation, metastable clusters, equilibrium thermodynamics, crystallization, mineral precipitation, water hardness, hypercapnia
- MeSH terms
- Calcification, Physiologic, Calcium, Calcium Carbonate, Carbonates, Crystallization, Hydrogen-Ion Concentration, Ions, Models, Chemical, Chemical Precipitation, Solutions, Thermodynamics, Molecular Structure, Chemical Phenomena
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