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Surface chemistry allows for abiotic precipitation of dolomite at low temperature
Open accessAbstract
Although the mineral dolomite is abundant in ancient low-temperature sedimentary systems, it is scarce in modern systems below 50 °C. Chemical mechanism(s) enhancing its formation remain an enigma because abiotic dolomite has been challenging to synthesize at low temperature in laboratory settings. Microbial enhancement of dolomite precipitation at low temperature has been reported; however, it is still unclear exactly how microorganisms influence reaction kinetics. Here we document the abiotic synthesis of low-temperature dolomite in laboratory experiments and constrain possible mechanisms for dolomite formation. Ancient and modern seawater solution compositions, with identical pH and pCO2, were used to precipitate an ordered, stoichiometric dolomite phase at 30 °C in as few as 20 d. Mg-rich phases nucleate exclusively on carboxylated polystyrene spheres along with calcite, whereas aragonite forms in solution via homogeneous nucleation. We infer that Mg ions are complexed and dewatered by surface-bound carboxyl groups, thus decreasing the energy required for carbonation. These results indicate that natural surfaces, including organic matter and microbial biomass, possessing a high density of carboxyl groups may be a mechanism by which ordered dolomite nuclei form. Although environments rich in organic matter may be of interest, our data suggest that sharp biogeochemical interfaces that promote microbial death, as well as those with high salinity may, in part, control carboxyl-group density on organic carbon surfaces, consistent with origin of dolomites from microbial biofilms, as well as hypersaline and mixing zone environments.
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In the paper
“In the MSW and SSW experiments, the differing sulfate content did not significantly impact precipitation of Mg-bearing carbonates.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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“Ancient and modern seawater solution compositions, with identical pH and pCO 2 , were used to precipitate an ordered, stoichiometric dolomite phase at 30 °C in as few as 20 d.”
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“HRTEM-based energy-dispersive X-ray (EDX) spectroscopy reveals a predominance of Mg-rich phases at sphere surfaces characteristic of both dolomite (Mg:Ca = 1) and a phase with Mg:Ca ratios greater than 1.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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In the paper
“All solutions were initially supersaturated with respect to calcite, aragonite, and dolomite (Table 1).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
What the sources say
- Not matchedcites Table 1
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In the paper
“Experimental vessels containing MSW produced aragonite and calcite.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
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In the paper
“For example, sedimentary settings with microbial activity promoting rapid cell turnover or death, such as a change from sulfate reduction to methanogenesis (32), can result in an order of magnitude increase in surface site density (33) on organic remains.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [32] 32. Meister P, et al. (2007) Dolomite formation in the dynamic deep biosphere: Results from the Peru Margin. Sedimentology 54(5):1007-1032. source
- Not checked — no full text of the sourcecites [33] 33. van der Wal A, Norde W, Zehnder AJB, Lyklema J (1997) Determination of the total charge in the cell walls of gram-positive bacteria. Colloids Surf 9(1-2):81-100. source
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In the paper
“Dehydration and carbonation of Mg ions are rate-limiting steps in dolomite nucleation (4).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [4] 4. Brady PV, Krumhans JL, Papenguth HW (1996) Surface complexation clues to dolo- mite growth. Geochim Cosmochim Acta 60(4):727-731. source
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“These results indicate that natural surfaces, including organic matter and microbial biomass, possessing a high density of carboxyl groups may be a mechanism by which ordered dolomite nuclei form.”
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In the paper
“Degraded natural organic matter (NOM) with a high fulvic acid character and certain microbial surfaces are known to have high carboxyl-group densities (Table 2).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not matchedcites Table 2
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In the paper
“Greater effect from carboxyl groups than sulfate is not surprising considering the association between Mg:R-COO -is more favorable than Mg:SO 4 based on aqueous complex data [log K MgSO4(aq) = 2.4; log K C10H16MgN2O8 = 2.8; 29].”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not matchedcites [29] 29. Motekaitis RJ, ed. (2004) NIST Critically Selected Stability Constants of Metal Com- plexes Data (v. 8.0 for Windows), National Institute of Standards and Technology.
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In the paper
“We propose that this sequence creates a thin dolomite template for further precipitation under continued supersaturated conditions (e.g., 9).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [9] 9. Mirsal IA, Zankl H (1985) Some phenomenological aspects of carbonate geochemistry. The control effect of transition metals. Geol Rundsch 74(2):367-377. source
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In the paper
“The results show that the changing chemistry of seawater through time has had a predictable effect on the distribution of dolomite and other marine minerals.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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“Because of the spatial association of dolomite exclusively with microsphere surfaces, we propose that natural low-temperature dolomite nucleates preferentially in the presence of carboxylated surfaces, such as certain types of organic matter with high carboxyl sites densities (>0.1 sites Å -2 ; Table 2).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not matchedcites Table 2
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In the paper
“This is consistent with other experimental findings (14) that demonstrate that sulfate inhibition (1) is not solely responsible for slow dolomite precipitation at low temperature.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [14] 14. Sánchez-Román M, McKenzie JA, Wagener A, Rivadeneyra MA, Vasconcelos C (2009) Presence of sulfate does not inhibit low-temperature dolomite formation. Earth Planet Sci Lett 285(1-2):131-139. source
- Not checked — no full text of the sourcecites [1] 1. Baker PA, Kastner M (1981) Constraints on the formation of sedimentary dolomite. Science 213(4504):214-216. source
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In the paper
“Absence of Mg-rich phases in control experiments is strong evidence supporting surface mediated nucleation of these phases.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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In the paper
“For example, the presence of iron oxides and clay minerals may concentrate carboxyl-rich organic carbon due to sorption (37).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [37] 37. McKnight DM, et al. (1992) Sorption of dissolved organic carbon by hydrous alumi- num and iron oxides occurring at the confluence of Deer Creek with the Snake River, Summit County, Colorado. Environ Sci Technol 26(7):1388-1396. source
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In the paper
“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).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
What the sources say
- Not checked — no full text of the sourcecites [24] 24. Roberts JA, Bennett PC, González LA, Macpherson GL, Milliken KL (2004) Precipitation of dolomite in methanogenic groundwater. Geology 32(4):277-280. source
- Partly supportedcites [3] 3. Arvidson RS, MacKenzie FT (1999) The dolomite problem: Control of precipitation kinetics by temperature and saturation state. Am J Sci 299:257-288. sourceExperimental — accuracy not yet measured
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)
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In the paper
“Our data indicate that the precipitated mineral suite is a function of solution composition, whereas surface carboxyl-group density dictated the kinetics of precipitation, with 10 sites Å -2 spheres (20.3 μm) exhibiting slightly faster precipitation kinetics (Fig. 1), and, in general, more crystalline Mg-bearing phases.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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In the paper
“Mg-rich phases nucleate exclusively on carboxylated polystyrene spheres along with calcite, whereas aragonite forms in solution via homogeneous nucleation.”
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“Scanning electron microscopy (SEM) and HRTEM analysis demonstrate that microspheres are thinly coated with minerals (Fig. 4) and serve as points of nucleation for nanocrystalline mineral aggregates (Fig. 5; see discussion below), whereas larger aragonite crystals (identified based on elemental analyses and crystal structure) precipitate in the pore space (Fig. 4).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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In the paper
“In all experimental vessels changes in pH and CO 3 2-values did not vary from the control within the error of measurement whereas values of Mg: Ca and degree of supersaturation for calcite, aragonite, and dolomite decreased (Fig. 1) more than control values after the 20-d period.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
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In the paper
“Control vessels for SSW produced aragonite (CaCO 3 ), and calcite (CaCO 3 ); control vessels for MSW produced only aragonite.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
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In the paper
“Acetic acid treatments revealed extremely low yields of Mg calcite (5-42 mol % Mg) and disordered dolomite (50-51mol % Mg and, 61-75 mol % Mg), likely due to Mg binding to the sphere surface, thus decreasing the available Mg in solution (25).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
What the sources say
- Not checked — no full text of the sourcecites [25] 25. Lippmann F (1973) Sedimentary Carbonate Minerals (Springer, New York), p 228. source
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In the paper
“Surface-associated carbonate precipitates form as nanoparticles with fine-scale layering, and HRTEM with selected area electron diffraction (SAED) of precipitates shows lattice fringes of 2.89 Å [211] (Fig. 6).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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In the paper
“All experimental vessels containing SSW produced aragonite and calcite, with a smaller peak that is consistent with dolomite (Fig. 2).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
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In the paper
“We have identified a viable abiotic mechanism for primary dolomite nucleation that relies on the carboxyl-group density of surfaces as a means to overcome the limitation of Mg dehydration and that such surfaces contribute to stabilization of nanocrystals, limiting dissolution, and promoting crystallinity.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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- The authors state this as an assumption: Carboxylated polystyrene microspheres are adequate models for natural organic surfaces, including microbial EPS, in dolomite nucleation.
In the paper
“This reaction lowers the energy needed for carbonation and the subsequent attachment of Ca 2+ when the Mg(H 2 O) 5 2+ complex is bound to an RCOO -group compared with dewatering and carbonation of Mg(H 2 O) 6 2+ (ΔG is 13.6 kcal mol -1 lower when Mg is dehydrated and bound to RCOO -; 28).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [28] 28. Katz AK, Glusker JP, Markham GD, Bock CW (1998) Deprotonation of water in the presence of carboxylate and magnesium ions. J Phys Chem B 102(33):6342-6350. source
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In the paper
“Our data support a surface-nucleated mechanism for EPS in the presence of supersaturated solutions and provide a quantifiable mechanism for the data and observed relationships between dolomite and EPS reported in the literature.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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In the paper
“Organic matter is a typical constituent of carbonate rocks and a potential source of carboxylated surfaces that can bind and dehydrate dissolved Mg ions (30) and facilitate dolomitization (Table 1).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [30] 30. Sikiri c MD, Füredi-Milhofer H (2006) The influence of surface active molecules on the crystallization of biominerals in solution. Adv Colloid Interface Sci 128-130:135-158. source
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In the paper
“Surface carboxyl functional groups, however, have been demonstrated to adsorb Mg 2+ enabling the formation of a [Mg(H 2 O) 5 (R-COO)] + complex, which results in the ejection of a water molecule (27):”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [27] 27. Kluge S, Weston J (2005) Can a hydroxide ligand trigger a change in the coordination number of magnesium ions in biological systems? Biochemistry 44(12):4877-4885. source
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In the paper
“Mixing zone environments (34) and changing-salinity environments such as sabkhas (35) may promote dolomitization via carboxyl-group density increases resulting from salinity changes (36).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [34] 34. Badiozamani K (1973) The Dorag dolomitization model-application to the Middle Ordovician of Wisconsin. J Sediment Petrol 43(4):965-984. source
- Not checked — no full text of the sourcecites [35] 35. Müller DW, McKenzie JA, Mueller PA (1990) Abu Dhabi sabkha Persian Gulf revisited: Application of strontium isotopes to test an early dolomitization model. Geology 18(7):618-662. source
- Not matchedcites [36] 36. Kinnebrew N (2012) Metal sorption onto halophilic Archaea. MS thesis (Univ of Kansas, Lawrence).
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In the paper
“We infer that Mg ions are complexed and dewatered by surface-bound carboxyl groups, thus decreasing the energy required for carbonation.”
What the sources say
- Not checked — no full text of the sourcecites [27] 27. Kluge S, Weston J (2005) Can a hydroxide ligand trigger a change in the coordination number of magnesium ions in biological systems? Biochemistry 44(12):4877-4885. source
- Not checked — no full text of the sourcecites [28] 28. Katz AK, Glusker JP, Markham GD, Bock CW (1998) Deprotonation of water in the presence of carboxylate and magnesium ions. J Phys Chem B 102(33):6342-6350. source
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In the paper
“Because our model does not require metabolic activity, only solution supersaturation achieved by any means, it extends beyond microbial surfaces as we propose that any type of organic matter with sufficient carboxyl-site density is capable of seeding dolomite precipitation.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
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In the paper
“Mg:Ca ratios less than 2, such as those thought to have existed in Cambrian-through-Devonian and Cretaceous seawater (21; and modeled with SSW solution in this study), promote calcite and dolomite precipitation.Mg:Ca ratios greater than 2, such as those thought to have existed in the Permo-Carboniferous, Triassic, and Neogene seawater (21; and modeled with MSW solution in this study) promote arag”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
What the sources say
- Not checked — no full text of the sourcecites [21] 21. Wilkinson BH, Given KR (1986) Secular variation in abiotic marine carbonates: con- straints on Phanerozoic atmospheric carbon dioxide contents and oceanic Mg/Ca ratios. J Geol 94(3):321-333. source
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In the paper
“Replicate experimental vessels were analyzed at 5, 10, and 20 d.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Materials and Methods
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- Based: passes — The paper gives a reason why it holds.
Probably not a substantial claim. The paper’s conclusions may not depend on it.
None of the sources cited for this claim have been checked yet.
In the paper
“Salinity and pCO 2 (speciated from measured pH and titrated alkalinity using PhreeqC; 23) were identical for both solutions (Table 1; 21).”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Materials and Methods
What the sources say
- Not matchedcites [23] 23. Parkhurst DL, Appelo CAJ (1999) PHREEQC v.2, USGS WRI Report 99-4259.
Couldn’t be matched to a paper in Crossref, so it can’t be checked.
- Not checked — no full text of the sourcecites [21] 21. Wilkinson BH, Given KR (1986) Secular variation in abiotic marine carbonates: con- straints on Phanerozoic atmospheric carbon dioxide contents and oceanic Mg/Ca ratios. J Geol 94(3):321-333. source
plain- Asserted: passes — The authors put it forward as true.
- Checkable: passes — It can be checked against evidence.
- Load-bearing: passes — The paper’s conclusions depend on it.
- Based: passes — The paper gives a reason why it holds.
Probably not a substantial claim. It may state two separate claims as one.
- Not matched
A conclusion the paper draws from its own results — it cites no other source for it, so there is none to check. The quote shows it is in the paper.
In the paper
“Although the presence of carboxylated surfaces facilitates precipitation of dolomite nuclei at low temperature, solution chemistry fundamentally controls the reactions.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
plaindirect- Asserted: passes — The authors put it forward as true.
- Checkable: passes — It can be checked against evidence.
- Load-bearing: passes — The paper’s conclusions depend on it.
- Based: passes — The paper gives a reason why it holds.
It may state two separate claims as one.
What the paper did — it cites no source for this, so there is none to check. The quote shows it is in the paper.
In the paper
“Control vessels contained no polystyrene spheres and were analyzed at 20 d.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Materials and Methods
plain- Asserted: passes — The authors put it forward as true.
- Checkable: passes — It can be checked against evidence.
- Load-bearing: fails — The paper’s conclusions may not depend on it.
- Based: passes — The paper gives a reason why it holds.
Probably not a substantial claim. The paper’s conclusions may not depend on it. It may state two separate claims as one.
A conclusion the paper draws from its own results — it cites no other source for it, so there is none to check. The quote shows it is in the paper.
In the paper
“Abiotic precipitation of low-temperature dolomite reported here clarifies geology's “dolomite problem,” and is not only consistent with, but identifies, mechanisms operative in previous studies implicating microorganisms in this process.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
boosteddirect- Asserted: passes — The authors put it forward as true.
- Checkable: passes — It can be checked against evidence.
- Load-bearing: passes — The paper’s conclusions depend on it.
- Based: passes — The paper gives a reason why it holds.
It may state two separate claims as one.
- The authors state this as an assumption: Carboxylated polystyrene microspheres are adequate models for natural organic surfaces, including microbial EPS, in dolomite nucleation.
What the paper did — it cites no source for this, so there is none to check. The quote shows it is in the paper.
In the paper
“Solutions were then sterilized and dispensed into 60-mL serum bottles.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Materials and Methods
plain- Asserted: passes — The authors put it forward as true.
- Checkable: passes — It can be checked against evidence.
- Load-bearing: fails — The paper’s conclusions may not depend on it.
- Based: passes — The paper gives a reason why it holds.
Probably not a substantial claim. The paper’s conclusions may not depend on it.
A conclusion the paper draws from its own results — it cites no other source for it, so there is none to check. The quote shows it is in the paper.
In the paper
“It may be that environments that lead to accelerated cell turnover or death, changing or high salinity, or certain settings of weathering product delivery may be the ones where highly carboxylated surfaces are generated.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
hedgedconditional- Asserted: passes — The authors put it forward as true.
- Checkable: passes — It can be checked against evidence.
- Load-bearing: passes — The paper’s conclusions depend on it.
- Based: fails — The paper may give no reason why it holds.
Probably not a substantial claim. The paper may give no reason why it holds. It may state two separate claims as one.
- The authors state this as an assumption: Carboxylated polystyrene microspheres are adequate models for natural organic surfaces, including microbial EPS, in dolomite nucleation.
A conclusion the paper draws from its own results — it cites no other source for it, so there is none to check. The quote shows it is in the paper.
In the paper
“It demonstrates the need to concentrate organic surface functional groups as seeds for dolomite nucleation, which would ultimately form the nuclei for more extensive dolomitization of carbonate rocks and sediments during later times of fluid migration.”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Dolomite Identification.
boosteddirect- Asserted: passes — The authors put it forward as true.
- Checkable: passes — It can be checked against evidence.
- Load-bearing: passes — The paper’s conclusions depend on it.
- Based: passes — The paper gives a reason why it holds.
It may state two separate claims as one.
- The authors state this as an assumption: Carboxylated polystyrene microspheres are adequate models for natural organic surfaces, including microbial EPS, in dolomite nucleation.
The authors state this as an assumption.
Carboxylated polystyrene microspheres are adequate models for natural organic surfaces, including microbial EPS, in dolomite nucleation.
“Here we report an example of abiotic laboratory precipitation of dolomite at 30 °C by nucleation on synthetic, carboxylated surfaces, used as models for natural organic surfaces including microbial EPS.”
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?
The source backs part of the claim, not all of it — or backs it for a different population, condition or comparison.
In the citing paper
“the main kinetic factors that inhibit the nucleation or precipitation of dolomite at low temperatures are thought to include: (1) the high hydration energy of the magnesium ion [22,45,51,66,[74][75][76][77][78][79][80]; (2) the presence of sulfate (even in very low concentrations), related to the formation of complex MgSO 4 0 [32,74,81,82]; and (3) the low activity of CO 2- 3 in most natural solut”
From Thermodynamic and Kinetic Studies of Dolomite Formation: A Review (2023) · cites this paper as [77]
Experimental — accuracy not yet measuredThe source backs part of the claim, not all of it — or backs it for a different population, condition or comparison.
In the citing paper
“Furthermore, carboxyl moieties within EPS matrix were identified as the major functional groups to accelerate Mg 2+ dehydration (Wang et al., 2009;Roberts et al., 2013;Zhang et al., 2015).”
From Catalytic effect of microbially-derived carboxylic acids on the precipitation of Mg-calcite and disordered dolomite: Implications for sedimentary dolomite formation (2020) · cites this paper as Roberts et al., 2013
Experimental — accuracy not yet measuredThe cited source says what the claim attributes to it.
In the citing paper
“In the first model, it has suggested that electronegative carboxyl functional groups can bind and partially dewater Mg 2+ -H2O complexes, generating Mg 2+ -carboxyl group complexes.”
From Experimental evidence for abiotic formation of low-temperature proto-dolomite facilitated by clay minerals (2019) · cites this paper as Roberts et al., 2013
The cited source says what the claim attributes to it.
In the citing paper
“Mg 2+ -carboxyl complex requires much lower energy for carbonation than Mg 2+ -H2O complex”
From Experimental evidence for abiotic formation of low-temperature proto-dolomite facilitated by clay minerals (2019) · cites this paper as Roberts et al., 2013
The cited source says what the claim attributes to it.
In the citing paper
“Importantly, Mg-carboxyl clusters require less energy for carbonation and subsequent attachment of Ca 2+ compared to Mg-H2O complexes (Kenward et al., 2013;Roberts et al., 2013;Qiu et al., 2017).”
From A non-classical crystallization mechanism of microbially-induced disordered dolomite (2024) · cites this paper as Roberts et al., 2013
The cited source says what the claim attributes to it.
In the citing paper
“Previous studies also proposed that the dehydration reaction induced by carboxyl moieties proceeds possibly via a metal-chelation mechanism (Romanek et al., 2009;Roberts et al., 2013).”
From Catalytic effect of microbially-derived carboxylic acids on the precipitation of Mg-calcite and disordered dolomite: Implications for sedimentary dolomite formation (2020) · cites this paper as Roberts et al., 2013
The cited source says what the claim attributes to it.
In the citing paper
“Specifically, the electronegative carboxyl groups bind to [Mg(H2O)6] 2+ ion pairs and form a [Mg(H2O)5(R-COO)] + complex, along with the ejection of one water molecule (Roberts et al., 2013).”
From Catalytic effect of microbially-derived carboxylic acids on the precipitation of Mg-calcite and disordered dolomite: Implications for sedimentary dolomite formation (2020) · cites this paper as Roberts et al., 2013
The cited source says what the claim attributes to it.
In the citing paper
“Upon the dewatering, the newly formed Mg-carboxyl complex requires significantly lower energy when binding CO3 2-than [Mg(H2O)6] 2+ (Roberts et al., 2013;Shen et al., 2014).”
From Catalytic effect of microbially-derived carboxylic acids on the precipitation of Mg-calcite and disordered dolomite: Implications for sedimentary dolomite formation (2020) · cites this paper as Roberts et al., 2013
The cited source says what the claim attributes to it.
In the citing paper
“In doing so, it is believed that a thin Ca-Mg carbonate template could form and its growth will take place when a supersaturated condition is maintained (Roberts et al., 2013).”
From Catalytic effect of microbially-derived carboxylic acids on the precipitation of Mg-calcite and disordered dolomite: Implications for sedimentary dolomite formation (2020) · cites this paper as Roberts et al., 2013
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.
Rated major: it would touch a result — a value a result rests on, reported and recomputed p-values on opposite sides of the significance level, two passages that conflict with no sign which is right, or a cited work retracted before this paper was published.
In the paper
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
“Here we report the abiotic synthesis of dolomite at 25 °C”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Materials and Methods
“The experimental vessels were capped and solution chemistry was allowed to evolve with gentle agitation in the dark at 30 °C for 20 d.”
Rated major: it would touch a result — a value a result rests on, reported and recomputed p-values on opposite sides of the significance level, two passages that conflict with no sign which is right, or a cited work retracted before this paper was published.
In the paper
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > Results and Discussion
“Acetic acid treatments revealed extremely low yields of Mg calcite (5-42 mol % Mg) and disordered dolomite (50-51mol % Mg and, 61-75 mol % Mg)”
§ Surface chemistry allows for abiotic precipitation of dolomite at low temperature > ACKNOWLEDGMENTS.
“Acetic acid leaching of precipitates from MSW treatments was below the detection limit of the instrument.”
Citations
Cites
An oscillating trend in Phanerozoic non-skeletal carbonate mineralogy
Sandberg, P. A. (1983) · Nature · doi:10.1038/305019a0 · Cited by 818 · cited 1×
“One solution represents conditions typical of modern seawater (MSW) favoring aragonite and high-Mg calcite precipitation (21), whereas the other broadly simulates Silurian seawater (SSW) in which calcite is the favored carbonate phase (22).”
BackgroundMicrobial mediation as a possible mechanism for natural dolomite formation at low temperatures
Vasconcelos, C., McKenzie, J. A., Bernasconi, S., Grujic, D., & Tiens, A. J. (1995) · Nature · doi:10.1038/377220a0 · Cited by 745 · cited 2×
“Laboratory precipitation at low temperature has only been successful in producing disordered dolomite: from solutions with high salinity (6); through intermittent (7) or complete dehydration (8); by using organic or inorganic compounds that effectively dewater Mg ions (9–11); or in the presence of microorganisms, thei…”
BackgroundConstraints on the Formation of Sedimentary Dolomite
Baker, P. A., & Kastner, M. (1981) · Science · doi:10.1126/science.213.4504.214 · Cited by 614
BRAISSANT, O., DECHO, A. W., DUPRAZ, C., GLUNK, C., PRZEKOP, K. M., & VISSCHER, P. T. (2007) · Geobiology · doi:10.1111/j.1472-4669.2007.00117.x · Cited by 590
Oscillations in Phanerozoic Seawater Chemistry: Evidence from Fluid Inclusions
Lowenstein, T. K., Timofeeff, M. N., Brennan, S. T., Hardie, L. A., & Demicco, R. V. (2001) · Science · doi:10.1126/science.1064280 · Cited by 585
Sedimentary Carbonate Minerals
Lippmann, F. (1973) · doi:10.1007/978-3-642-65474-9 · Cited by 545
The dolomite problem; control of precipitation kinetics by temperature and saturation state
Arvidson, R. S. (1999) · American Journal of Science · doi:10.2475/ajs.299.4.257 · Cited by 447 · cited 2×
“Kinetic inhibition is attributed to lack of solution supersaturation (3), sulfate inhibition (1), cation desolvation (4), and lack of nucleation sites (5).”
BackgroundMicrobial Polysaccharides Template Assembly of Nanocrystal Fibers
Chan, C. S., De Stasio, G., Welch, S. A., Girasole, M., Frazer, B. H., Nesterova, M. V., Fakra, S., & Banfield, J. F. (2004) · Science · doi:10.1126/science.1092098 · Cited by 423
McKnight, D. M., Bencala, K. E., Zellweger, G. W., Aiken, G. R., Feder, G. L., & Thorn, K. A. (1992) · Environmental Science & Technology · doi:10.1021/es00031a017 · Cited by 405
The dorag dolomitization model, application to the middle Ordovician of Wisconsin
Badiozamani, K. (1973) · Journal of Sedimentary Research · doi:10.1306/74d728c9-2b21-11d7-8648000102c1865d · Cited by 384
Research works printed but not linked: 2
- Kinnebrew N (2012) Metal sorption onto halophilic Archaea. MS thesis (Univ of Kansas Lawrence).
- , eds LS Clesceri, AE Greenberg, AD Eaton (American Public Health Association, 20th Ed, Washington, DC) Standard Methods for Examination of Water & Wastewater, pp. 1325 (1999).
Cited by
Sorted by citations
A critical review of mineral-microbe interaction and co-evolution: Mechanisms and applications
Dong, H., Huang, L., Zhao, L., Zeng, Q., Liu, X., Sheng, Y., Shi, L., Wu, G., Jiang, H., Li, F., et al. (2022) · National Science Review · doi:10.1093/nsr/nwac128 · Cited by 472
“Abiotic precipitation of dolomite is even possible, as long as Mg2+ is released from ion pairs or a hydrated state [64,65].”
BackgroundMicrobially catalyzed dolomite formation: From near-surface to burial
Petrash, D. A., Bialik, O. M., Bontognali, T. R. R., Vasconcelos, C., Roberts, J. A., McKenzie, J. A., & Konhauser, K. O. (2017) · Earth-Science Reviews · doi:10.1016/j.earscirev.2017.06.015 · Cited by 338
“…formed under a suboxic condition, with nucleation promoted by the presence carboxyl-rich EPS probably secreted by phototrophic organisms (i.e., Roberts et al., 2013; Qiu et al., 2017), and subsequent stabilization enhanced by elevated and sustained alkalinity generation and pH produced by…”
BackgroundInfluentialSelf-citationOxygen and carbon isotope fractionation in the system dolomite–water–CO2 to elevated temperatures
Horita, J. (2014) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2013.12.027 · Cited by 298
Herlinger, R., Zambonato, E. E., & Ros, L. F. D. (2017) · Journal of Sedimentary Research · doi:10.2110/jsr.2017.70 · Cited by 218
“The formation of early dolomite was probably directly related to the dissolution of stevensite, although it may have been favored also by the dehydration of magnesium complexes promoted by the carboxylated surfaces of the organic matter present in the stevensite (Roberts et al. 2013).”
BackgroundBacteria-induced mineral precipitation: a mechanistic review
Hoffmann, T. D., Reeksting, B. J., & Gebhard, S. (2021) · Microbiology · doi:10.1099/mic.0.001049 · Cited by 206
“For example, in the precipitation of the calcium- magnesium mineral dolomite, the dehydration of the magnesium ion and subsequent carbonation are the rate- limiting step of nucleation [50].”
Background
Metadata
- Authors
- Roberts, J. A., Kenward, P. A., Fowle, D. A., Goldstein, R. H., González, L. A., & Moore, D. S.
- Affiliations
- University of Kansas (US)
- Department of Geology and
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2013-08-20
- Volume
- 110
- Issue
- 36
- Pages
- 14540-14545
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC3767548
- OpenAlex
- W2066115290
- Cited by
- 246
- References
- 40
- Citations by year
- 2026: 14 · 2025: 21 · 2024: 23 · 2023: 24 · 2022: 18 · 2021: 30 · 2020: 15 · 2019: 24 · 2018: 13 · 2017: 13 · 2016: 21 · 2015: 10 · 2014: 20
- FWCI
- 6.49
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- Europe PMC (PubMed Central) (publishedVersion, other-oa)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- 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
- surface chemistry, carboxyl groups, polystyrene microspheres, magnesium complexation, carbonation, nucleation, calcite, aragonite, biofilm, dolomite origin, seawater chemistry, reaction kinetics
- MeSH terms
- Bacteria, Calcium Carbonate, Carbon Dioxide, Environmental Microbiology, Hydrogen-Ion Concentration, Magnesium, Microscopy, Electron, Scanning, Models, Chemical, Chemical Precipitation, Seawater, Spectrometry, X-Ray Emission, Surface Properties, Temperature, X-Ray Diffraction, Bioreactors, Salinity
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.
A language model drew the claims from the paper on 2026-10-11, under version 3 of the claim definition (model deepseek-v4.1-flash, prompt extract-v3).
A second model labelled each claim on 2026-10-11 (model jev-1.13-20260917, definition revision gold-guideline-v0.2).
Cited sources are checked with a language model’s help (gpt-6-sol).
Statistics and arithmetic are recomputed, not judged.
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