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

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

Open access
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.

AI snapshot

Written from the paper’s full text.

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.

Model-written summary. Check it against the paper before relying on it.

Integrity signals

Registry

Crossref · 10.2475/ajs.299.4.257

Cites

46 of 46 references verified0 citation errors · 0 not checkable

Statistics

Nothing to recompute.

Claims the paper makes

0 of 47 cited sources checked · 0 supported · 0 flagged

  • Findingown data

    The pre-exponential term of the dolomite precipitation rate law is log A = 1.05.

    “moderate dependency on saturation index (n ‫؍‬ 2.26, log A ‫؍‬ 1.05)”
    Quote in the paperNot a substantial claim
    • 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.
    • The authors state this as an assumption: The rate constant k has an Arrhenius form.
  • Findingown data

    The precipitation rate of dolomite has a moderate dependency on saturation index, with reaction order n = 2.26.

    “moderate dependency on saturation index (n ‫؍‬ 2.26, log A ‫؍‬ 1.05)”
    Quote in the paperSubstantial claim
    • 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.
    • The authors state this as an assumption: The rate constant k has an Arrhenius form.
  • Findingown data

    The precipitation reaction of dolomite has a strong temperature dependence, with activation energy εA = 31.9 kcal mol−1.

    “These experiments do confirm a strong temperature dependence for the precipitation reaction (activation energy ⑀ A ‫؍‬ 31.9 kcal mol ؊1 )”
    Quote in the paperSubstantial claim
    • 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.
    • The authors state this as an assumption: The rate constant k has an Arrhenius form.
  • Findingown data

    At the highest supersaturations obtained, formation of distinct nucleation centers was observed.

    “At the highest supersaturations obtained, formation of distinct nucleation centers was observed.”
    Quote in the paperNot a substantial claim
  • Findingown data

    Coprecipitated phases, including calcite, magnesian calcite, and magnesite, were also identified by SEM/EDS and XRD.

    “Coprecipitated phases, including calcite, magnesian calcite, and magnesite (MgCO 3 ), were also identified by SEM/EDS and XRD.”
    Quote in the paperNot a substantial claim
  • May combine two claims. 39
  • Classified as probably not a substantial claim. 41
  • The quote only partly states this claim. 1

  • May combine two claims.

    Findingown data

    The dolomite produced in these experiments was variable in composition but typically a calcium-rich protodolomite, forming syntaxial overgrowths on the seed material.

    “The dolomite produced in these experiments was variable in composition but typically a calcium-rich protodolomite, forming syntaxial overgrowths on the seed material.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing). The quote only partly states this claim.

    Findingown data

    Dolomite heteronuclei were somewhat more calcium-rich, having between 53.2 and 58.5 percent CaCO3.

    “Dolomite heteronuclei were somewhat more calcium-rich, having between 53.2 to 58.5 percent”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingown data

    Backscatter SEM shows some contrast between newly crystallizing dolomite and magnesian calcite, allowing the two phases to be distinguished.

    “Backscatter SEM also shows some contrast between newly crystallizing dolomite and magnesian calcite, allowing the two phases to be distinguished (fig.5, top row).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    Run Ti01 is the only experiment in which magnesite developed, and magnesite was observed only epitaxially, not in apparent crystallographic continuity either with the dolomite substrate or dolomite phase overgrowths thereof.

    “This experiment (run Ti01) is the only one in which magnesite developed, and magnesite was observed only epitaxially, that is, not in apparent crystallographic continuity either with the dolomite substrate or dolomite phase overgrowths thereof.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingown data

    SEM/EDS analysis indicated these flecks to be μm-sized particles of Fe, Ni, or Cr, probably contributed from the preheater tubing loop.

    “SEM/EDS analysis indicated these to be µm-sized particles of Fe, Ni, or Cr, probably contributed from the preheater tubing loop.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    Dolomite heteronuclei were somewhat more calcium-rich, with CaCO3 compositions between 53.2 and 58.5%, and some spot analyses slightly greater than 60% CaCO3.

    “Dolomite heteronuclei were somewhat more calcium-rich, having between 53.2 to 58.5 percent CaCO 3 , with some spot analyses encountering compositions slightly greater than 60 percent CaCO 3 .”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

    Findingown data

    Syntaxial overgrowth of the substrate in run Ti01 was visible as the infilling of etch pits and the formation of a bumpy, irregular surface, compositionally indistinguishable under EDS from unreacted substrate material.

    “Syntaxial overgrowth of the substrate in this run was visible as the infilling of etch pits and the formation of a bumpy, irregular surface, compositionally indistinguishable under EDS from unreacted substrate material.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The run at 170°C shows an incremental uptake of calcium and magnesium, but total alkalinity data indicate dissolution at this temperature.

    “The run at 170°C shows an incremental uptake of calcium and magnesium; however, the total alkalinity data indicate dissolution at this temperature.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

    Findingown data

    These inclusions were not observed in reacted grains and presumably dissolved during reaction.

    “These inclusions were not observed in reacted grains and presumably dissolved during reaction.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingnone given

    Syntaxial growth of new dolomite predominates in all samples except those reacted at high supersaturation, where it is also accompanied by coprecipitated phases (magnesian calcite and magnesite).

    “Syntaxial growth of new dolomite predominates in all samples except those reacted at high supersaturation, where it is also accompanied by coprecipitated phases (magnesian calcite and magnesite).”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingown data

    Growth was most commonly developed as thinly aggregated terraces.

    “Growth was most commonly developed as thinly aggregated terraces (fig.3, top row).”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingown data

    Samples retrieved after lengthy reaction times at high temperatures were also typically discolored with small flecks of material.

    “Samples retrieved after lengthy reaction times at high temperatures were also typically discolored with small flecks of material.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingown data

    Acid washing prior to reaction resulted in dissolution in the form of rounding of interfacial angles, subhedral boundaries, and development of etch pits.

    “Acid washing prior to reaction resulted in dissolution in the form of rounding of interfacial angles, subhedral boundaries, and development of etch pits (fig.2).”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingown data

    SEM imaging also indicated a trace contribution of Fe and Mn in the form of oxide and silicate inclusions.

    “SEM imaging also indicated a trace contribution of Fe and Mn in the form of oxide and silicate inclusions.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    At high supersaturations, larger rhombic crystals form via aggregation of submicro-sized nuclei, in addition to possible secondary nuclei forming on the seed surface.

    “At high supersaturations, in addition to what may be secondary nuclei forming on the seed surface, larger rhombic crystals form via the aggregation of submicro-sized nuclei.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    These data show that log rate is a strong function of saturation index, which in turn mostly reflects the change in carbonate ion availability.

    “This effect is at least partly borne out by these data, in which the log ratefoot_3 is a strong function of saturation index, which in turn mostly reflects the change in carbonate ion availability.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    Spot EDS analyses of new dolomite from run Ti10 (170°-196°C) show it to be calcium-rich in composition, in agreement with fluid chemistry data.

    “Spot EDS analyses of what is clearly new dolomite to run Ti10 (170°-196°C, fig. 3) do show it to be calcium-rich in composition, in agreement with the fluid chemistry data.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

    Findingown data

    The variation in EDS analyses suggests variability in surface composition, and the data were fairly reproducible.

    “The variation in these EDS analyses also suggests variability in the surface composition, and although part of this variability may be an artifact of the instrument's semi-quantitative resolution, the data were nonetheless fairly reproducible.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The dolomite overgrowths formed in these experiments are not simply magnesian calcites; ~15 mol percent magnesian calcite did form but is identifiable from XRD and SEM data as a distinct, although clearly metastable, phase.

    “They are not simply magnesian calcites-ϳ15 mol percent magnesian calcite did form but is identifiable from XRD and SEM data as a distinct, although clearly metastable, phase.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    Regression of all data causes the order to diminish to 1.88 but increases the log frequency term to 2.09.

    “Regression of all data (including those derived from the literature) causes the order to diminish to 1.88 but increases the log frequency term by more than an order of magnitude to 2.09.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    The time required shortens considerably if starting concentration of MgCl2 is increased to 0.05 m; however, tens of years are still required at 25°C.

    “The time required shortens considerably if the starting concentration of MgCl 2 is increased to 0.05 m; however, tens of years are still required at 25°C.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    No distinct trends could be found in terms of evolution in composition of the newly precipitating solid, although the approach to a steady state reaction was variable in duration and direction.

    “Although the approach to a steady state reaction was variable in duration and direction, no distinct trends could be found in terms of evolution in composition of the newly precipitating solid.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingreasoning

    The growth of magnesian calcites (~15 mole percent MgCO3) where observed appears to outcompete dolomite for available dissolved components, and thus largely buffers dolomite precipitation subsequent to its appearance.

    “The growth of magnesian calcites (ϳ15 mole percent MgCO 3 ) where observed appears to outcompete dolomite for available dissolved components, and thus largely buffers dolomite precipitation subsequent to its appearance.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Premisecitation

    Modern dolomite exists but is common only in certain environments: marginal, restricted, hypersaline regimes; nonmarine lakes; and zones of microbial sulfate reduction.

    “Modern dolomite does indeed exist but is common only in certain environments: (1) marginal, restricted, hypersaline regimes such as the Coorong lakes of South Australia (Alderman, 1959), supratidal lagoons on the island of Bonaire, Netherland Antilles (Deffeyes, Lucia, and Weyl, 1965), and the sabkhas of the Persian Gulf (Wells, 1962)”
    Quote in the paperSubstantial claim0 of 3 sources checked
    • cites Alderman, 1959

      Couldn’t be matched to a paper in Crossref, so it can’t be checked.

    • cites Deffeyes, Lucia, and Weyl, 1965

      Couldn’t be matched to a paper in Crossref, so it can’t be checked.

    • cites Wells, 1962 source

  • Classified as probably not a substantial claim.

    Premisecitation

    Arvidson and Mackenzie (1997) computed dolomite growth rates and solution saturation states from published dolomite synthesis experiments.

    “In a preliminary effort to place the few laboratory data available into a meaningful framework, Arvidson and Mackenzie (1997) computed dolomite growth rates and solution saturation states from published dolomite synthesis experiments.”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Arvidson and Mackenzie (1997) source

  • Classified as probably not a substantial claim.

    Premisecitation

    The relationship between dolomite growth rates and solution saturation states was expressed as a rate law consistent with the hypothesis that the rate of dolomite precipitation is a function of temperature and solution composition.

    “The relationship between these two independent pieces of information was expressed as a rate law consistent with the hypothesis that the rate of dolomite precipitation is a function of temperature and solution composition.”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Arvidson and Mackenzie (1997) source

  • Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

    Premisecitation

    Malone, Baker, and Burns (1996) observed that the rate of recrystallization of initially disordered (Ca,Mg)-carbonates was a strong function of temperature, and temperature increases produced corresponding increases in MgCO3 and cation ordering.

    “In more recent work, Malone, Baker, and Burns (1996) observed that the rate of recrystallization of initially disordered (Ca,Mg)-carbonates was a strong function of temperature, and temperature increases produced corresponding increases in MgCO 3 and cation ordering.”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites Malone, Baker, and Burns (1996) source

  • May combine two claims.

    Interpretationcitation

    The rate derived by Peterson et al. is exceedingly slow, and dolomite crystals growing at this rate would require 200 Ma to acquire an edge length of 1 mm.

    “This rate is exceedingly slow, and dolomite crystals growing at this rate would require 200 Ma to acquire an edge length of 1 mm.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Premisecitation

    Dolomite is found in environments ranging from the shallow subtidal to supratidal.

    “Dolomite is also found in environments ranging from the shallow subtidal (Mazzullo, Bischoff, and Teal, 1995) to supratidal (Carballo, Land, and Miser, 1987).”
    Quote in the paperNot a substantial claim0 of 2 sources checked
    • cites Mazzullo, Bischoff, and Teal, 1995

      Couldn’t be matched to a paper in Crossref, so it can’t be checked.

    • cites Carballo, Land, and Miser, 1987 source

  • Classified as probably not a substantial claim. May combine two claims.

    Premisecitation

    Relatively modest increases in temperature and seawater saturation state could potentially give rise to large increases in the overall rate of dolomite precipitation and a substantial convergence of the relative rates of calcite and dolomite.

    “We also concluded that relatively modest increases in temperature and seawater saturation state could potentially give rise to large increases in the overall rate of dolomite precipitation and a substantial convergence of the relative rates of calcite and dolomite.”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Arvidson and Mackenzie (1997) source

  • Probably not a substantial claim: may not pass S4 (based).

    Premisenone given

    Rates cannot be meaningfully compared without simultaneous measurement of prevailing physico-chemical conditions.

    “In addition, rates cannot be meaningfully compared without simultaneous measurement of prevailing physico-chemical conditions.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Premisecitation

    These metastable calcium-rich, imperfectly ordered materials are distinct from magnesium calcite, which was the purpose of Graf and Goldsmith's (1956) original introduction of the term protodolomite.

    “It should be emphasized that these materials, despite their metastability, are distinct from magnesium calcite, and this was the purpose of Graf and Goldsmith's (1956) original introduction of the term protodolomite.”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites Graf and Goldsmith's (1956) source

  • Classified as probably not a substantial claim.

    Premisecitation

    Precipitation rates computed from the Arvidson and Mackenzie model agreed closely with age estimates in case studies of sabkha and organogenic dolomite of Recent to Pleistocene age.

    “Precipitation rates computed from this model agreed closely with age estimates in case studies of sabkha and organogenic dolomite of Recent to Pleistocene age.”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Arvidson and Mackenzie (1997) source

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Premisecitation

    Brady, Krumhansl, and Papenguth (1996) concluded that dehydration and carbonation of magnesium was the most probable rate-limiting step at low temperatures.

    “In adsorption experiments at room temperature and fixed pCO 2 , Brady, Krumhansl, and Papenguth (1996) concluded that dehydration and carbonation of magnesium was the most probable rate-limiting step at low temperatures.”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites Brady, Krumhansl, and Papenguth (1996) source

  • May combine two claims.

    Premisecitation

    The value of 31.9 kcal mol−1 is lower than the value of 42.1 kcal mol−1 obtained from Gaines (1968) and lower still than the published value of 49 kcal mol−1 from Katz and Matthews (1977).

    “The value of 31.9 kcal mol Ϫ1 is also lower than the value of 42.1 kcal mol Ϫ1 obtained from an analysis of unpublished data from Gaines (1968, rates computed from 220° 250°C; see also Arvidson and Mackenzie, 1997) which in turn is lower still than the only published value of 49 kcal mol Ϫ1 , determined from rates at temperatures from 252° to 295°C by Katz and Matthews (1977).”
    Quote in the paperNot a substantial claim0 of 3 sources checked
    • cites Gaines (1968)

      Couldn’t be matched to a paper in Crossref, so it can’t be checked.

    • cites Arvidson and Mackenzie, 1997 source
    • cites Katz and Matthews (1977) source

  • May combine two claims.

    Premisecitation

    Gaines (1968) observed an increase in MgCO3 with increasing temperature (220°-250°C), and the same effect at fixed temperature (200 and 220°C) as the ratio of magnesium to calcium in solution was increased from 0.5 to 1.0.

    “Gaines (1968) also observed an increase in MgCO 3 with increasing temperature (220°-250°C), although the same effect in his experiments could be observed at fixed temperature (200 and 220°C) as the ratio of magnesium to calcium in solution was increased from 0.5 to 1.0 (his table 2, p. 30).”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites Gaines (1968)

      Couldn’t be matched to a paper in Crossref, so it can’t be checked.

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Interpretationown data

    The alignment of magnesian calcite and dolomite rhombs suggests an underlying crystallographic control by the substrate.

    “The alignment of magnesian calcite and dolomite rhombs suggests an underlying crystallographic control by the substrate.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductnone given

    The precision in total alkalinity measurements was often poorer (approximately 0.3 percent) than that of total divalent cations (<0.1 percent).

    “Although the precision in total alkalinity measurements was often poorer (ϳ0.3 percent) than that of total divalent cations (Ͻ0.1 percent), most experiments were conducted in solutions whose total cation concentration was an order of magnitude greater than the total alkalinity.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductreasoning

    The leverage from the greater total cation concentration often made total alkalinity the quantity of choice in rate calculations.

    “This leverage often made total alkalinity the quantity of choice in rate calculations.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationown data

    Precipitation of magnesian calcite can occur at the expense of dolomite and apparently can also drive dissolution of newly formed, soluble dolomite.

    “which suggests that precipitation of magnesian calcite can occur at the expense of dolomite and apparently can also drive dissolution of newly formed, soluble dolomite.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Premisecitation

    The stoichiometry of recrystallized dolomite tends to improve with increasing temperature, and the composition of first-formed dolomite phases at any temperature tends to be richer in calcium compared to subsequent phases (50°-200°C).

    “The stoichiometry of recrystallized dolomite also tends to improve with increasing temperature, and the composition of first-formed dolomite phases at any temperature tends to be richer in calcium compared to subsequent phases (50°-200°C, Malone, Baker, and Burns, 1996).”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites Malone, Baker, and Burns, 1996 source

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Interpretationreasoning

    It is possible that the lower activation energy observed reflects a reduced energy barrier to forming calcian dolomites.

    “It is thus possible that the lower activation energy observed reflects a reduced energy barrier to forming calcian dolomities.”
    Quote in the paperNot a substantial claim

  • Classified as probably not a substantial claim. May combine two claims.

    Study design and conductnone given

    The reactor used in these experiments is similar in design to flow reactors used in solubility and kinetic studies of other minerals and is capable of measuring slow precipitation reactions at moderately elevated temperature and confining pressure.

    “Thereactor used in these experiments is similar in design to flow reactors used in solubility and kinetic studies of other minerals and is capable of measuring slow precipitation reactions at moderately elevated temperature and confining pressure.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Interpretationreasoning

    To some extent the variability in the new dolomite phase could be related to the conditions of the experiment.

    “To some extent this variability could be related to the conditions of the experiment, as described below.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductown data

    There was no indication from surface imaging that these contaminants interfered with growth of new material.

    “there was no indication from surface imaging that they interfered with growth of new material.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductown data

    ICP-ES analysis of reacted solutions from a single run at 150°C could not detect these elements.

    “ICP-ES analysis of reacted solutions from a single run at 150°C could not detect these elements.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationreasoning

    Had the reactor maintained a truly constant saturation index independent of temperature and reaction rate, measured rates at higher temperatures would most likely have been higher, giving a greater slope and higher computed activation energy.

    “Had the reactor been capable of maintaining a truly constant saturation index independent of temperature and reaction rate, measured rates at the higher temperatures would most likely have been higher still, giving a greater slope in figure 9, and thus a higher computed activation energy.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Interpretationnone given

    Changes in the dominant reaction mechanism with temperature may give rise to corresponding changes in activation energy, visible as changes in slope in figure 9.

    “Last, changes in the dominant reaction mechanism with temperature may give rise to corresponding changes in activation energy, visible as changes in slope in figure 9.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductown data

    These data agreed with additional EGTA/EDTA determinations of Ca and Mg in the seed dolomite.

    “These data agreed with additional EGTA/ EDTA determinations of Ca and Mg in the seed dolomite.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationown data

    Energies using divalent cation data yield substantially lower energies, larger uncertainties, and poorer fits and can be safely discarded because they are less than calcite on a per mole-CO3 basis.

    “Energies using the divalent cation data yield substantially lower energies, larger uncertainties, and poorer fits and can be safely discarded on the basis that they are less than calcite (on a per mole-CO 3 basis).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationreasoning

    Increases in rate due to temperature brought about increased consumption of reactants, which depressed the ion activity product and probably depressed the rate.

    “Increases in the rate by virtue of temperature also brought about increased consumption of reactants, which in turn served to depress the ion activity product and in turn probably depressed the rate.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductown data

    The computed d-spacing of the primary and secondary diffraction peaks agreed with the entry for ideal dolomite obtained from the JCPDF database to the precision of the instrument.

    “The computed d-spacing of the primary 510146 1 and secondary diffraction peaks agreed with the entry for ideal dolomite obtained from the JCPDF database to the precision of the instrument.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductown data

    Initial testing of the reactor by mounting surface thermocouples showed thermal gradients of less than 1°C over the reaction volume during recycle operation at temperatures up to approximately 200°C.

    “Initial testing of the reactor by mounting surface thermocouples showed thermal gradients of less than 1°C over the reaction volume during recycle operation at temperatures up to ϳ200°C.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Study design and conductown data

    These data (with few exceptions) reflect a more or less constant ratio of calcium to magnesium and thus are inadequate to evaluate how the rate may be influenced by changes in cation ratio, or by other influences such as ionic strength.

    “These data (with few exceptions) reflect a more or less constant ratio of calcium to magnesium and thus are inadequate to evaluate how the rate may be influenced by changes in cation ratio, or by other influences such as ionic strength”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationreasoning

    Both the cation disorder and solubility of the surface dolomite phase of these experiments are higher than the underlying substrate.

    “It is indeed likely that both the cation disorder and solubility of the surface dolomite phase of these experiments are higher than the underlying substrate”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Interpretationown data

    This lack of significant differences may simply reflect the difficulty of resolving phases insufficiently different in composition.

    “However, this may simply reflect the difficulty of resolving phases insufficiently different in composition.”
    Quote in the paperNot a substantial claim

  • Classified as probably not a substantial claim.

    Premisecitation

    In earlier synthesis work (Arvidson and Mackenzie, 1997), dolomite is formed through reaction of CaCO3 and (Ca,Mg)Cl2 solutions.

    “This observation is direct contrast to earlier synthesis work, discussed in Arvidson and Mackenzie (1997), in which dolomite is formed through reaction of CaCO 3 and (Ca,Mg)Cl 2 solutions.”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Arvidson and Mackenzie (1997) source

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Premisecitation

    Lippmann (1973) postulated that activated carbonate ions accelerate the rate of magnesite growth.

    “Lippmann (1973) has carried this model somewhat further in postulating that it is the influence of ''activated'' carbonate ions that accelerate the rate of magnesite growth.”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites Lippmann (1973)

      Couldn’t be matched to a paper in Crossref, so it can’t be checked.

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductnone given

    No provision is made for errors in saturation state calculations.

    “No provision is made for errors in saturation state calculations.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationreasoning

    The growth of sedimentary dolomite under conditions of greatly elevated alkalinity concentrations may not be purely a matter of grossly elevated supersaturations and implies additional dependencies, perhaps on the ratio of Mg2+ to Ca2+ activity.

    “The growth of sedimentary dolomite under conditions of greatly elevated alkalinity concentrations, for example by way of sulfate reduction, thus may not be purely a matter of grossly elevated supersaturations and implies additional dependencies, perhaps on the ratio of Mg 2ϩ to Ca 2ϩ activity, not explicitly described by the rate law in its current form.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationcitation

    The time required for reaction at ~50°C, although still lengthy, is not unreasonable, in qualitative agreement with results of Malone, Baker, and Burns (1996).

    “Note however, that the time required for reaction at ϳ50°C, although still lengthy, are not unreasonable, in qualitative agreement with the results of Malone, Baker, and Burns (1996).”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites Malone, Baker, and Burns (1996) source

  • May combine two claims.

    Interpretationcitation

    These layers closely resemble those developed in published calcite growth kinetics experiments and imply a mechanism of polynuclear growth, in which surfaces accrete through growth, spread, and coalescence of multiple nucleation points.

    “These layers closely resemble those developed in published calcite growth kinetics experiments (compare figs. 3 and 4 with 9, Shiraki and Brantley, 1995) and imply a mechanism of polynuclear growth, in which the surfaces accrete through the growth, spread, and coalescence of multiple nucleation points.”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Shiraki and Brantley, 1995 source

  • May combine two claims.

    Premisecitation

    Poor cation ordering and excess calcium are hallmarks of Holocene dolomite.

    “However, poor cation ordering and excess calcium are hallmarks of Holocene dolomite as well, as discussed in Arvidson (1998).”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Arvidson (1998)

      Couldn’t be matched to a paper in Crossref, so it can’t be checked.

  • May combine two claims.

    Interpretationnone given

    In a 0.5 m matrix of NaCl, decrease in activity coefficients and increased complexation retard the rate further.

    “In a 0.5 m matrix of NaCl, decrease in activity coefficients and increased complexation retard the rate further.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Study design and conductnone given

    Errors for all rates (except those from published hydrothermal bomb experiments) have been estimated by combining titration errors with uncertainty in activation energy using standard propagation of error.

    “Errors for all rates (except those computed from published hydrothermal bomb experiments) have been estimated by combining the titration errors with the uncertainty in the activation energy value using standard propagation of error.”
    Quote in the paperNot a substantial claim

  • Classified as probably not a substantial claim.

    Interpretationreasoning

    If the rate of dolomite growth is fundamentally limited by incorporation of magnesium in the MgCO3 layer, then its activation energy would be related to those of magnesium-bearing single carbonates.

    “If the rate of dolomite growth is fundamentally limited by the incorporation of magnesium in the MgCO 3 layer, then one would expect its activation energy to be related to those of the magnesium-bearing single carbonates.”
    Quote in the paperSubstantial claim
    • The authors state this as an assumption: The rate of dolomite growth is fundamentally limited by the incorporation of magnesium in the MgCO3 layer.

  • May combine two claims.

    Study design and conductreasoning

    The values obtained by regression for parameters are sensitive to errors in observables, and the computed model rate will be sensitive to parameter values chosen from regression.

    “The values obtained by regression for these parameters are sensitive to errors in the observables (rates and saturation indices), and the computed model rate will thus also be sensitive to the parameter values chosen from the regression analysis.”
    Quote in the paperNot a substantial claim

  • Classified as probably not a substantial claim.

    Study design and conductown data

    Data judged to be of poor quality were excluded from the regression treatment.

    “It should be noted that data judged to be of poor quality, either because of problems with the reactor itself or because of uncertainties regarding the effect of coprecipitating phases, were excluded from this treatment.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationown data

    The dolomite forming in these experiments is most likely protodolomite, sensu Graf and Goldsmith (1956), with a solubility greater than that of the underlying dolomite substrate.

    “Based on these compositions, comparison of activation energy, and evidence of dissolution in certain runs, the dolomite forming in these experiments is most likely protodolomite, sensu Graf and Goldsmith (1956), with a solubility greater than that of the underlying dolomite substrate.”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites Graf and Goldsmith (1956) source

  • May combine two claims.

    Interpretationreasoning

    Mg2+ dehydration is a major component of activation energy, with the remaining energy involved in cation ordering.

    “Comparison of these energies with those estimated from a comparison of hydration enthalpies of Ca 2ϩ versus Mg 2ϩ suggests that Mg 2ϩ dehydration is a major component of activation energy, with the remaining energy involved in cation ordering.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Interpretationown data

    Such developments are possibly twins with shared axes.

    “raising the possibility that such developments are twins with shared axes.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationreasoning

    Extrapolations to laboratory conditions suggest infeasibly long reaction times at 25°C, but with significant improvement at slightly higher temperatures.

    “Extrapolations to laboratory conditions suggest infeasibly long reaction times at 25°, but with significant improvement at slightly higher temperatures.”
    • Also stated in: § CONCLUSIONS · hedged
      “The times estimated for 25°C reactions (10 1 to 10 2 yrs) suggest that direct laboratory observation under these conditions is infeasible.”
    Quote in the paperSubstantial claim

  • Classified as probably not a substantial claim.

    Interpretationreasoning

    Past environmental shifts may have altered the fluxes of magnesium to carbonate versus basalt reservoirs.

    “However, if the abundance of dolomite reflects its absolute precipitation rate in the environment, the high sensitivity of the rate to changes in temperature and seawater chemistry raises the possibility that past environmental shifts have altered the fluxes of magnesium to carbonate versus basalt reservoirs.”
    Quote in the paperSubstantial claim
    • Rests on an assumption: The abundance of dolomite reflects its absolute precipitation rate in the environment.

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Premisecitation

    Recent work tends to be largely dismissive of the importance of dolomite.

    “Although the control and history of seawater composition has long been of interest, recent work tends to be largely dismissive of the importance of dolomite (Hardie, 1996;Stanley and Hardie, 1998).”
    Quote in the paperNot a substantial claim0 of 2 sources checked
    • cites Hardie, 1996 source
    • cites Stanley and Hardie, 1998 source
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

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • Previous works have noted an increasing dolomitization rate with higher alkalinity in all experiments.

    “Previous works have also noted an increasing dolomitization rate with higher alkalinity in all experiments.69−71”

    From Low-Temperature Synthesis of Disordered Dolomite and High-Magnesium Calcite in Ethanol–Water Solutions: The Solvation Effect and Implications (2022) · cites this paper as [71]

    In “Relevance of Experimental Results to Natural Carbonate Minerals” (page unavailable), the paper says its measured dolomite precipitation rate depends strongly on saturation index, which mostly reflects carbonate-ion availability. This supports the general alkalinity–rate relationship, but not the claim that the rate increased with higher alkalinity in all experiments; the paper describes the experimental effect as only “at least partly borne out” and reports that calcite growth could severely diminish dolomite precipitation. (LLM, conf=0.86)

    Experimental — accuracy not yet measured

  • The conversion of very high-Mg calcite to dolomite may take a long time under ambient conditions, but this may not be long on a geologic timescale.

    “It is possible that the process takes a long time under ambient conditions [72,132,144], but this may not be long on a geologic timescale.”

    From Thermodynamic and Kinetic Studies of Dolomite Formation: A Review (2023) · cites this paper as [144]

    The ‘Relevance of Experimental Results to Natural Carbonate Minerals’ section estimates tens to hundreds of years for dolomite precipitation at 25°C, and the Introduction contrasts laboratory experiments with the age of Recent natural dolomite. Those passages support a long ambient-timescale process that may be short geologically, but they do not establish the claim’s specific process of converting very high-Mg calcite to dolomite. The Conclusions instead report no evidence that magnesian calcite acts as a reactive intermediate. (LLM, conf=0.84)

    Experimental — accuracy not yet measured

  • Non-classical crystallization can be seen as a preliminary step prior to nucleation of the crystalline step, which may occur to overcome kinetic barriers.

    “Thus, the non-classical crystallization can be seen as a preliminary step prior to the nucleation of the crystalline step, which may occur to overcome the kinetic barriers.37,56”

    From Mechanisms of Mg carbonates precipitation and implications for CO <sub>2</sub> capture and utilization/storage (2023) · cites this paper as [37]

    The Methods and ‘Relevance of Experimental Results to Natural Carbonate Minerals’ sections (pages not provided) describe small nuclei coalescing into larger dolomite crystals. They do not describe non-classical crystallization as a step before nucleation or say that this sequence overcomes kinetic barriers. (LLM, conf=0.82)

    Experimental — accuracy not yet measured

  • Acetic acid treatment of SSW precipitates revealed low yields of Mg calcite (19-49 mol % Mg) and disordered (64-75 mol % Mg) and ordered dolomite.

    “Precipitates treated with weak acetic acid to remove Ca carbonates (e.g., 24) revealed low yields [based on Xray diffraction (XRD) intensity] of Mg calcite (19-49 mol % Mg; calculated from XRD with 3; % MgCO 3 = [(-363.96*d-spacing)+ 1,104.5])and disordered (64-75 mol % Mg; calculated from XRD with 3) and ordered dolomite [CaMg(CO 3 ) 2 ] (Fig. 3).”

    From Surface chemistry allows for abiotic precipitation of dolomite at low temperature (2013) · cites this paper as [3]

    The Methods passage describes calculating Mg-calcite composition from XRD d-spacing and gives a regression close to the one cited, though its intercept is 1104.05 rather than 1104.5. It does not establish the cited XRD method for calculating disordered-dolomite composition. The SSW yields and composition ranges are the citing paper’s reported results, not findings attributed to this source. (LLM, conf=0.84)

    Experimental — accuracy not yet measured

  • One crystallization mechanism does not exclude the other.

    “It is also important to note that one mechanism does not exclude the other.37”

    From Mechanisms of Mg carbonates precipitation and implications for CO <sub>2</sub> capture and utilization/storage (2023) · cites this paper as [37]

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

Cites

Flagged first, then by citations

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.

Cited by

Sorted by citations

Related

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

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Claims read by deepseek-v4.1-flash under definition version 3 (extract-v3) on 2026-10-11.

Classified by jev-1.13-20260917 (gold-guideline-v0.2) on 2026-10-11.

Statistics and arithmetic are recomputed, not judged.

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