Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate
Open accessAbstract
Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus ) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC⇒anhydrous ACC ∼ biogenic anhydrous ACC⇒vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO 2 sequestration.
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The thermodynamic stability (enthalpy) of less-disordered and anhydrous ACC is greater than that of more-disordered and hydrated ACC, therefore dehydration and ordering of ACC is likely thermodynamically driven.
“Radha et al. (2010) showed that the thermodynamic stability (enthalpy) of less-disordered and anhydrous ACC is greater than that of more-disordered and hydrated ACC, therefore the dehydration and ordering of the ACC is likely to be thermodynamically driven (lowering of enthalpy in the system).”
From A route for the direct crystallization of dolomite (2015) · cites this paper as Radha et al. 2010
The morphology (spherical) and size (44 ± 13 nm) of the starting Mg-ACC were similar to that reported for ACC.
“The morphology (spherical) and size (44 ± 13 nm) of our starting Mg-ACC were also similar to that reported for ACC (e.g., Radha et al. 2010, sample ACC-5, Ø 50-100 nm; Bots et al. 2012, ACC, Ø ~ 40 nm).”
From A route for the direct crystallization of dolomite (2015) · cites this paper as Radha et al. 2010
This is akin to behavior observed for pure ACC where prior to crystallization an increase in ordering of the amorphous phase was likely accompanied by a lowering in water content and a final transformation to a fully anhydrous amorphous phase.
“This is akin to the behavior observed for pure ACC (Radha et al. 2010; Bots et al. 2012) where prior to crystallization an increase in ordering of the amorphous phase was also likely accompanied by a lowering in water content and a final transformation to a fully anhydrous amorphous phase.”
From A route for the direct crystallization of dolomite (2015) · cites this paper as Radha et al. 2010
Because amorphous calcium carbonate is less thermodynamically stable than crystalline CaCO3, its higher solubility product increases Ca2+ concentration in the pore solution, which lowers the driving force for C-(N)-A-S-H gel decomposition.
“With respect to AAS, since ACC is less thermodynamically stable than crystalline CaCO348, the higher solubility product of ACC increases Ca2+ concentration in the pore solution, which lowers the driving force for C-(N)-A-S-H gel decomposition39.”
From Spatially resolved nanostructural analysis of disordered phases in carbonated alkali-activated slag (2025) · cites this paper as [48]
Since ACC is metastable but less thermodynamically favorable than crystalline calcium carbonate, the equilibrium of dissolution favors a higher concentration of Ca2+ in solution where ACC is present, which reduces the driving force for decalcification of the C-(N)-A-S-H gel.
“Since ACC is metastable but less thermodynamically favorable than crystalline calcium carbonate48, the equilibrium of dissolution favors a higher concentration of Ca2+ in solution where ACC is present, which reduces the driving force for decalcification of the C-(N)-A-S-H gel.”
From Spatially resolved nanostructural analysis of disordered phases in carbonated alkali-activated slag (2025) · cites this paper as [48]
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- Authors
- Radha, A. V., Forbes, T. Z., Killian, C. E., Gilbert, P. U. P. A., & Navrotsky, A.
- Affiliations
- University of California, Davis (US)
- University of Wisconsin–Madison (US)
- Corresponding author
- Navrotsky, Alexandra
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2010-09
- Volume
- 107
- Issue
- 38
- Pages
- 16438-16443
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC2944757
- OpenAlex
- W2153265189
- Cited by
- 509
- References
- 4
- Citations by year
- 2026: 39 · 2025: 38 · 2024: 36 · 2023: 30 · 2022: 47 · 2021: 29 · 2020: 27 · 2019: 42 · 2018: 20 · 2017: 35 · 2016: 25 · 2015: 34 · 2014: 35 · 2013: 26 · 2012: 25
- FWCI
- 9.51
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Foundation (DEAC02-05CH11231, 0613972)
- U.S. Department of Energy (-AC02-05CH11231, DE‐FG02‐, FG02-07ER15899, 05CH11231, DE AC02 05CH11231, DEFG0207ER15899, DE-AC02-)
- Office of Science (DEAC02–05CH11231, AC02-05CH11231, DE-AC02)
- University of California, Davis
- Division of Chemistry (DE-AC02-05CH11231)
- Basic Energy Sciences (DE-AC02, DE-AC02-05CH11231., DE-FG02, AC02–05CH11231, DE-FG02–07ER15899)
- 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
- amorphous calcium carbonate, metastability, dehydration, calcite, aragonite, vaterite, biomineralization, Strongylocentrotus purpuratus, enthalpy, free energy, CO2 sequestration, calcite precipitation
- MeSH terms
- Animals, Calcium Carbonate, Calorimetry, Differential Scanning, Crystallization, Chemical Precipitation, Thermodynamics, Spectroscopy, Fourier Transform Infrared, Powder Diffraction, Strongylocentrotus purpuratus
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