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Cited by 449Calcium Carbonate Crystallization and InhibitionGeochemistry and Elemental AnalysisCO2 Sequestration and Geologic Interactions

The DOI matches its Crossref record; 44 of the 44 references it cites were found in a registry or an index; none of the 47 sources its claims cite is checked for support yet.

The dolomite problem; control of precipitation kinetics by temperature and saturation state

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Arvidson, R. S.·1999·American Journal of Science
DOI 10.2475/ajs.299.4.257
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Abstract

The mineral dolomite and the uncertainties surrounding its origin have attracted the attention of earth scientists for over a century. The core of the dolomite problem is the apparent paradox posed by the paucity of dolomite in modern marine depositional environments versus its relative abundance in the sedimentary rock record. Solving this problem requires knowledge of the conditions under which the mineral forms and the rate of precipitation under those conditions. As a working hypothesis, it is suggested that the precipitation rate of dolomite may be quantified and modeled in a manner similar to other carbonate minerals through application of a rate law that represents the rate as a simple function of saturation index, r = k (Omega - 1) ^n^ . This hypothesis is tested in a series of experiments by measuring the steady state rate of dolomite precipitation in a dolomite-seeded flow reactor through analysis of reacted fluid chemistry. By varying temperature from approx 100 degrees to 200 degrees C and saturation index (Omega ) from near saturation to approximately 100, sufficient data were collected to solve for the reaction order and Arrhenius rate constant (k = A exp {-(epsilon ~A~ /RT)}) of this rate law. The dolomite produced in these experiments was variable in composition but typically a calcium-rich protodolomite, forming syntaxial overgrowths on the seed material. At the highest supersaturations obtained, formation of distinct nucleation centers was observed. These experiments do confirm a strong temperature dependence for the precipitation reaction (activation energy epsilon ~A~ = 31.9 kcal mol (super -1) ) and moderate dependency on saturation index (n = 2.26, log A = 1.05). The experimental findings of this paper suggest that the abundance of dolomite in the sedimentary rock record reflects, at least in part, environmental changes in temperature and seawater chemistry over geologic time.

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TL;DR

This paper tests whether dolomite precipitation can be described by a simple saturation-state rate law, using seeded flow-reactor experiments at elevated temperatures. It finds a strong temperature dependence and moderate saturation-state dependence, implying that dolomite abundance in the rock record may partly reflect past changes in temperature and seawater chemistry.

Key findings

  • Dolomite precipitation rates fit an Arrhenius-type rate law, with activation energy of 31.9 ± 1.6 kcal mol⁻¹ from total-alkalinity data, reaction order n = 2.26, and log A = 1.05 for the selective fit; the extrapolated 25°C rate constant is 10⁻²²·³.
  • The precipitated phase was typically calcium-rich protodolomite, commonly 55–58 mol percent CaCO₃, forming syntaxial overgrowths on seed grains; distinct nucleation centers appeared only at high supersaturation, around log(Ω − 1) ≥ 2.
  • Magnesian calcite, about 15 mol percent MgCO₃, competed with dolomite and appeared to precipitate at dolomite’s expense, even driving dissolution of newly formed dolomite; the paper found no evidence that magnesian calcite acted as a precursor.
  • Model extrapolations indicate that observing enough dolomite growth at 25°C would require roughly 10¹ to 10² years, making direct laboratory synthesis at surface temperatures impractical, while reaction times at about 50°C are still long but less unreasonable.

Methods

  • A dolomite-seeded, circulating flow reactor was used with about 5 g of seed dolomite, temperatures from 115° to 196°C, input solutions of CaCl₂, MgCl₂, and NaHCO₃ under varied pCO₂, and a recycle ratio up to about 100.
  • Steady-state precipitation rates were calculated from differences between input and output solution chemistry, mainly total alkalinity and total divalent cations, normalized to seed surface area; solids were analyzed by XRD, SEM/EDS, and BET or geometric surface-area estimates.
  • An aqueous speciation model using SUPCRT92/HKF thermodynamics computed saturation states with respect to ideal dolomite, and regressions solved for activation energy, reaction order, and the pre-exponential factor.

Limitations

  • Stated: the Arrhenius treatment assumes terms other than temperature are invariant, but this is not exact; saturation states were calculated relative to ideal dolomite even though the growing phase was likely more soluble and less ordered; high solid-to-solution ratios caused saturation indices to fall as temperature rose, so the reported activation energy is probably a minimum.
  • Stated: the dataset is small, surface-area estimates are uncertain, geometric and BET areas were mixed, possible Fe/Ni/Cr contamination had unknown kinetic effects, and coprecipitating phases could reduce the area available for dolomite growth.
  • Evident from the text: the experiments were conducted far above Earth-surface temperatures, so the 25°C conclusions depend on extrapolation; the rate law does not explicitly account for Mg/Ca ratio or ionic strength, and variability in product composition and cation ordering may affect rates.

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Integrity signals

Registry

Crossref · 10.2475/ajs.299.4.257

Cites

44 of 44 references verified0 citation errors · 0 not checkable

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Verification

Claims the paper makes

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Show all 122 claims

  • It may state two separate claims as one. 39
  • Probably not a substantial claim. 41
  • The quote only partly states this claim. 1
74 of 74

  • The authors state this as an assumption.

    The precipitation rate of dolomite can be described by a rate law of the form r = k(Ω − 1)^n.

    “As a working hypothesis, it is suggested that the precipitation rate of dolomite may be quantified and modeled in a manner similar to other carbonate minerals through application of a rate law that represents the rate as a simple function of saturation index, r ‫؍‬ k(⍀ ؊ 1) n .”

  • The authors state this as an assumption.

    The rate constant k has an Arrhenius form.

    “The rate constant k is assumed to have an Arrhenius form,”

  • The authors state this as an assumption.

    The reactive surface area S is equivalent to the total surface area of the seed material.

    “S, hereafter assumed equivalent to total surface area”

  • The paper relies on this without support.

    The meager distribution of Recent dolomite contrasts strongly with its common abundance in ancient sedimentary rocks of marine origin, producing the dolomite problem.

    “The meager distribution of Recent dolomite contrasts strongly with its common abundance in ancient sedimentary rocks of marine origin, leading to the paradox commonly referred to as the ''dolomite problem.''”

  • The paper relies on this without support.

    Surface seawater is strongly oversaturated with respect to ideal dolomite, and yet there is little evidence of widespread dolomite precipitation in modern, open marine sediments.

    “Surface seawater is strongly oversaturated with respect to ideal dolomite (CaMg(CO 3 ) 2 ), and yet there is little evidence of widespread dolomite precipitation in modern, open marine sediments.”

  • The paper relies on this without support.

    There is a general consensus that the dearth of Recent dolomite reflects a kinetic control.

    “There is a general consensus that the dearth of Recent dolomite reflects a kinetic control, but there are very few measurements of rates of dolomite growth from either field or laboratory settings.”

  • The authors state this as an assumption.

    Corrections for pH electrode drift can be made by assuming the slope and intercept are linear functions of time.

    “Corrections due to drift in the electrode's calibration were made by assuming the slope and intercept to be linear functions of time t, and interpolating pH(t) appropriately.”

  • The authors state this as an assumption.

    The terms represented by the ellipsis in eq (8) are invariant over the experimental temperature span.

    “The ellipsis in eq (8) encumbers terms assumed to be invariant over this span of temperature.”

  • The authors state this as an assumption.

    The reaction is driven by the distance from equilibrium with respect to ideal dolomite, not by a phase rendered more soluble by calcium enrichment and cation disordering.

    “Second, we have made the assumption that it is the distance from equilibrium with respect to ideal dolomite and not a phase rendered more soluble by calcium enrichment and cation disordering that drives this reaction.”

  • The authors state this as an assumption.

    The mechanism of growth is identical in magnesite and calcite, and thus the values for frequency factor and reaction order are identical.

    “If we assume that the mechanism of growth is identical in both minerals (and thus that the values for frequency factor and reaction order are identical)”

  • The authors state this as an assumption.

    Dolomite growth can be viewed as a process of constructing alternating layers of calcite and magnesite.

    “If dolomite growth is viewed as a process of constructing alternating layers of calcite and magnesite”

  • The authors state this as an assumption.

    At a given temperature, dehydration of calcium requires less energy than magnesium.

    “If, at a given temperature, dehydration of calcium requires less energy than magnesium”

  • The authors state this as an assumption.

    The rate of dolomite growth is fundamentally limited by the incorporation of magnesium in the MgCO3 layer.

    “If the rate of dolomite growth is fundamentally limited by the incorporation of magnesium in the MgCO 3 layer”

  • The authors state this as an assumption.

    Ordering in the relatively well-ordered dolomites synthesized by Gaines (1968) is essentially perfect.

    “If ordering in the latter case is assumed to be essentially perfect”

  • The authors state this as an assumption.

    The change in activation energy with MgCO3 content is linear.

    “A linear relationship is assumed for the change in activation energy with MgCO 3 , using energies for calcite (Kazmierczak, Tomson, and Nancollas, 1982) and magnesite (computed from Lippmann, 1973).”

  • The authors state this as an assumption.

    The entry for logr + εA/2.3RT assumes an activation energy value of 31.9 kcal mol−1.

    “The entry for logr ϩ ⑀ A /2.3 RT assumes an activation energy value of 31.9 kcal mol Ϫ1 computed from run Ti10.”

  • The authors state this as an assumption.

    Both regression lines assume an activation energy of 31.9 kcal mol−1.

    “Both lines assume an activation energy of 31.9 kcal mol Ϫ1 .”

  • The authors state this as an assumption.

    The difference in solubility between the product surface phase and ideal dolomite is not a function of temperature.

    “If we make the dubious assumption that this difference in solubility is not a function of temperature”

  • The authors state this as an assumption.

    The coprecipitated phase is a calcian dolomite with 57 percent CaCO3.

    “assuming a calcian dolomite (57 percent CaCO 3 )”

  • The authors state this as an assumption.

    Magnesium dehydration is the controlling step for the activation energy of the dolomite phase formed in this experiment.

    “predicted by assuming magnesium dehydration to be the controlling step”

  • The authors state this as an assumption.

    Sufficient measurements are feasible to apply classical nucleation and crystal growth theory to dolomite.

    “assuming that sufficient measurements are feasible.”

  • The paper relies on this without support.

    The abundance of dolomite reflects its absolute precipitation rate in the environment.

    “if the abundance of dolomite reflects its absolute precipitation rate in the environment”
22 of 22

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Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

Each contradiction between two passages listed here was confirmed by an independent check.

  • Katz and Matthews activation energy is given as both 49 and 48

    Minor

    The text calls 49 kcal/mol the published Katz and Matthews value, but later identifies 48 kcal/mol as the value taken from that publication for the model fits.

  • Temperature-normalization formula omits the logarithm conversion factor

    Minor

    The final note specifies log r + εA/RT for comparing rates across temperatures, while Table 5 specifies log r + εA/(2.3 RT). For the base-10 logarithms used in the rate law, these are different normalizations.

2 of 2

Citations

Cites

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Show all 43 references

Research works printed but not linked: 7

  1. [3]3. Arvidson, R. S., ms, 1998, The kinetics of dolomite precipitation with application to changes in seawater saturation state over the past 100 Ma: Ph.D. thesis, Honolulu, The University of Hawaii, 320 p.
  2. [9]9. Bischoff, W. D., ms, 1985, Magnesian calcites; physical and chemical properties and stabilities in aqueous solution of synthetic and biogenic phases: Ph.D. thesis, Northwestern University, Evanston, 144 p.
  3. [11]11. Busenberg, E., and Plummer, L. N., 1986, A comparative study of the dissolution and crystal growth kinetics of calcite and aragonite, in Mumpton, F. A., editor, Studies in Diagenesis: U. S. Geological Survey Bulletin B 1578, p. 139-168.
  4. [16]16. Deffeyes, K. S., Lucia, F. J., and Weyl, P. K., 1965, Dolomitization of recent and Plio-Pleistocene sediments by marine evaporite water on Bonaire, Netherland Antilles, in Pray, L. C., and Murray, R. C., editors, Dolomitization and Limestone Diagenesis: A Symposium: Society of Economic Paleontologists and Mineralogists Publication no. 13, p. 71-88.
  5. [18]18. Gaines, A. M., ms, 1968, An Experimental Investigation of the Kinetics and Mechanism of the Formation of Dolomite: Ph.D. thesis, Chicago, The University of Chicago, 83 p.
  6. [35]35. Lippmann, F., 1973, Sedimentary Carbonate Minerals, Minerals, Rocks and Inorganic Materials, Monograph Series of Theoretical and Experimental Studies, v. 4: Berlin, Springer-Verlag, 228 p.
  7. [40]40. Morse, J. W., and Mackenzie, F. T., 1990, Geochemistry of Sedimentary Carbonates, Vol. 48 of Developments in Sedimentology: Amsterdam, Elsevier, 707 p.

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Metadata

Authors
Arvidson, R. S.
Affiliations
University of Hawaiʻi at Mānoa (US)
Corresponding author
Arvidson, R. S.
ORCID
Arvidson, R. S.
Venue
American Journal of Science
Publisher
American Journal of Science (AJS)
Published
1999-04-01
Volume
299
Issue
4
Pages
257-288
ISSN
0002-9599 (ISSN-L)
DOI
10.2475/ajs.299.4.257
OpenAlex
W2017918382
Semantic Scholar
a7089a5eff292400fe9e9a919119e166bfc231c5
Cited by
447
References
43
Citations by year
2026: 27 · 2025: 26 · 2024: 26 · 2023: 33 · 2022: 17 · 2021: 26 · 2020: 28 · 2019: 27 · 2018: 21 · 2017: 30 · 2016: 20 · 2015: 17 · 2014: 17 · 2013: 23 · 2012: 16
FWCI
5.06
Type
journal article
Language
en
Open access
Locations
American Journal of Science (publishedVersion)
Funders
American Chemical Society Petroleum Research Fund
Topics
  • Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
  • Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
  • Physical Sciences › Environmental Science › Environmental Engineering › CO2 Sequestration and Geologic Interactions
Keywords
dolomite problem, saturation index, temperature dependence, activation energy, Arrhenius rate constants, reaction order, protodolomite, syntaxial overgrowths, nucleation, dolomite origin, carbonate precipitation, seawater chemistry

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