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Cited by 147CO2 Sequestration and Geologic InteractionsCalcium Carbonate Crystallization and InhibitionNanopore and Nanochannel Transport Studies

Molecular-scale mechanisms of CO2 mineralization in nanoscale interfacial water films

Open access
Abdolhosseini Qomi, M. J., Miller, Q. R. S., Zare, S., Schaef, H. T., Kaszuba, J. P., Rosso, K. M.·2022·Nature Reviews Chemistry
DOI 10.1038/s41570-022-00418-1
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Abstract

The calamitous impacts of unabated carbon emission from fossil-fuel-burning energy infrastructure call for accelerated development of large-scale CO 2 capture, utilization and storage technologies that are underpinned by a fundamental understanding of the chemical processes at a molecular level. In the subsurface, rocks rich in divalent metals can react with CO 2, permanently sequestering it in the form of stable metal carbonate minerals, with the CO 2-H 2 O composition of the post-injection pore fluid acting as a primary control variable. In this Review, we discuss mechanistic reaction pathways for aqueous-mediated carbonation with carbon mineralization occurring in nanoscale adsorbed water films. In the extreme of pores filled with a CO 2-dominant fluid, carbonation reactions are confined to angstrom to nanometre-thick water films coating mineral surfaces, which enable metal cation release, transport, nucleation and crystallization of metal carbonate minerals. Although seemingly counterintuitive, laboratory studies have demonstrated facile carbonation rates in these low-water environments, for which a better mechanistic understanding has come to light in recent years. The overarching objective of this Review is to delineate the unique underlying molecular-scale reaction mechanisms that govern CO 2 mineralization in these reactive and dynamic quasi-2D interfaces. We highlight the importance of understanding unique properties in thin water films, such as how water dielectric properties, and consequently ion solvation and hydration behaviour, can change under nanoconfinement. We conclude by identifying important frontiers for future work and opportunities to exploit these fundamental chemical insights for decarbonization technologies in the twenty-first century.

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Crossref · 10.1038/s41570-022-00418-1

Cites

234 of 234 references verified0 citation errors · 0 not checkable

Statistics

Nothing to recompute.

Claims the paper makes

19 of 94 cited sources checked · 8 supported · 0 flagged · accuracy not yet measured

  • Premisecitation

    Magnesite formation has been reported at 25-35 °C and 90 bar, compared to ~65 °C necessary for uncatalyzed formation in bulk water environments.

    “Magnesite formation has been reported at only 25-35 °C and 90 bar 60 49 61 , compared to ~65 °C necessary for uncatalyzed formation in bulk water environments, a barrier attributed to notoriously sluggish Mg 2+ water exchange kinetics.49,62,63”
    Quote in the paperSubstantial claim1 of 3 sources checked
    • cites [60] Qafoku, O. et al. Formation of submicron magnesite during reaction of natural forsterite in H2O-saturated supercritical CO2. Geochim. Cosmochim. Acta 134, 197–209 (2014). source
    • cites [49] Felmy, A. R. et al. Reaction of water-saturated supercritical CO2 with forsterite: evidence for magnesite formation at low temperatures. Geochim. Cosmochim. Acta 91, 271–282 (2012). source
    • cites [61] Mergelsberg, S. T. et al. Low temperature and limited water activity reveal a pathway to magnesite via amorphous magnesium carbonate. Chem. Commun. 56, 12154–12157 (2020). This study expanded the temperature of abiotic magnesite precipitation in thin water films down to ambient temperature while hinting at amorphous carbonate phase stabilization in low water activity interfaces. source

      The Figure 2 caption reports magnesite formation at 25 °C and 90 bar, and the introduction describes earlier formation at 35 °C in thin water films. The introduction says magnesite is rarely observed below 60 °C in aqueous solution, likely because of slow Mg²⁺ water exchange; it does not establish that ~65 °C is necessary for uncatalyzed formation in bulk water or give 90 bar for the 35 °C result. (LLM, conf=0.86)

      Experimental — accuracy not yet measured
  • Premisecitation

    The dissolution of quartz increases with increasing pH because Si-O-Si bond breakage is facilitated by hydroxyls.

    “Conversely, the dissolution of quartz (SiO2), the structure of which is based entirely on Si-O-Si bridges, increases with increasing pH 117 because Si-O-Si bond breakage is facilitated by hydroxyls.118,119”
    Quote in the paperNot a substantial claim1 of 3 sources checked
    • cites [117] Palandri, J. L. & Kharaka, Y. K. A compilation of rate parameters of water–mineral interaction kinetics for application to geochemical modeling. DTIC https://apps.dtic.mil/docs/citations/ADA440035 (2004). source
    • cites [118] Dove, P. M. & Crerar, D. A. Kinetics of quartz dissolution in electrolyte solutions using a hydrothermal mixed flow reactor. Geochim. Cosmochim. Acta 54, 955–969 (1990). source
    • cites [119] Dove, P. M., Han, N. & Yoreo, J. J. D. Mechanisms of classical crystal growth theory explain quartz and silicate dissolution behavior. Proc. Natl Acad. Sci. USA 102, 15357–15362 (2005). source

      The Methods report that the quartz experiments used input solutions at circumneutral pH, while the Results examine saturation state and added salts—not increasing pH. A separate passage says pH strongly controls silicate dissolution rates, but gives no direction for quartz. The hydroxyl-mediated bond-breakage explanation is attached to other citations in the citing sentence. (LLM, conf=0.74)

      Experimental — accuracy not yet measured
  • Premisecitation

    Forsterite-to-magnesite carbonation has apparent activation energies of 34±7 kJ/mol at 100% RH and 83±17 kJ/mol at 85% RH.

    “Miller et al. 46,137 measured time-dependent forsterite to magnesite carbonation at different temperatures, and determined apparent activation energies of 34±7 kJ/mol at 100% RH and 83±17 kJ/mol at 85% RH, Figure 7.”
    Quote in the paperSubstantial claim2 of 2 sources checked
    • cites [46] Miller, Q. R. S. et al. Anomalously low activation energy of nanoconfined MgCO3 precipitation. Chem. Commun. 55, 6835–6837 (2019). The first study to quantify carbonation kinetics in thin water films, and the temperature dependence of the reaction rate suggested that the nanoconfined Mg2+ hydration configuration is responsible for facile magnesite precipitation in thin water films relative to the bulk. source

      The results section reports an apparent activation energy of 36±6 kJ/mol for magnesite precipitation in ~1 nm water films from 50–90 °C, using forsterite reacted with water-saturated CO₂. That supports the general measurement described, but not the quoted 34±7 kJ/mol value; our copy also does not report an 85% RH measurement or 83±17 kJ/mol. (LLM, conf=0.86)

      Experimental — accuracy not yet measured
    • cites [137] Miller, Q. R. S. et al. Emerging investigator series: ion diffusivities in nanoconfined interfacial water films contribute to mineral carbonation thresholds. Environ. Sci. Nano 7, 1068–1081 (2020). This is the first study of carbonation activation energy as a function of water film thickness, in conjunction with molecular simulation, and revealed that ion diffusion controls carbonation reactivity thresholds. source
  • Premisecitation

    Forsterite dissolution increases monotonically with decreasing pH.

    “Forsterite dissolution increases monotonically with decreasing pH.111,112”
    Quote in the paperSubstantial claim1 of 2 sources checked
    • cites [111] Rimstidt, J. D., Brantley, S. L. & Olsen, A. A. Systematic review of forsterite dissolution rate data. Geochim. Cosmochim. Acta 99, 159–178 (2012). source
    • cites [112] Oelkers, E. H., Declercq, J., Saldi, G. D., Gislason, S. R. & Schott, J. Olivine dissolution rates: a critical review. Chem. Geol. 500, 1–19 (2018). source
  • Premisecitation

    The ~67 kJ/mol reduction of the energy barrier is much larger than the ~16 kJ/mol difference between the Mg2+ and Ca2+ transition energy barriers from solvent-separated to monodentate contact ion-pair states.

    “For example, the ~67 kJ/mol reduction of the energy barrier is much larger than the ~16 kJ/mol 131 difference between the Mg 2+ and Ca 2+ transition energy barriers from solvent-separated to monodentate contact ion-pair states.”
    Quote in the paperSubstantial claim1 of 1 sources checked
    • cites [131] Raiteri, P., Demichelis, R. & Gale, J. D. Thermodynamically consistent force field for molecular dynamics simulations of alkaline-earth carbonates and their aqueous speciation. J. Phys. Chem. C 119, 24447–24458 (2015). source
  • May combine two claims. 29
  • Classified as probably not a substantial claim. 13

  • May combine two claims.

    Premisecitation

    Adsorbed water nanofilms can readily mediate the nucleation and growth of metastable intermediates, including nesquehonite, hydromagnesite, aragonite, and amorphous Mg/Ca carbonates, as well as facilitate transformations of carbonate minerals, including dolomite recrystallization and hydrated calcite surface dissolution.

    “Although structurally and dimensionally highly-constrained, adsorbed water nanofilms can readily mediate the nucleation and growth of metastable intermediates, including nesquehonite (MgCO3•3H2O) 55 , hydromagnesite [Mg5(CO3)4(OH)2•4H2O] 50 , aragonite (CaCO3) 56 , and amorphous Mg/Ca carbonates, 53,57 as well as facilitate transformations of carbonate minerals, including dolomite [CaMg(CO3)2] rec”
    Quote in the paperSubstantial claim2 of 3 sources checked
    • cites [55] Miller, Q. R. S. et al. Tunable manipulation of mineral carbonation kinetics in nanoscale water films via citrate additives. Environ. Sci. Technol. 52, 7138–7148 (2018). source

      Split into 2 atoms — 0 confirmed, 2 partially supported, 0 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.

      Experimental — accuracy not yet measured
    • cites [50] Schaef, H. T. et al. Forsterite [Mg2SiO4)] carbonation in wet supercritical CO2: an in situ high-pressure X-ray diffraction study. Environ. Sci. Technol. 47, 174–181 (2013). source
    • cites [56] Chai, Y. E. et al. Pressurized in situ X-ray diffraction insights into super/subcritical carbonation reaction pathways of steelmaking slags and constituent silicate minerals. J. Supercrit. Fluids 171, 105191 (2021). source

      Split into 2 atoms — 0 confirmed, 1 partially supported, 0 disputed, 0 misattributed, 1 unverifiable. Expand the claim to see per-atom verdicts.

      Experimental — accuracy not yet measured

  • May combine two claims.

    Premisecitation

    Two years after injections, the Wallula pilot project and the Carbfix project have reported 60% and between 72-95% mineralization of injected CO2, respectively.

    “Two years after injections, the Wallula pilot project and the Carbfix project have reported 60% (293 tonnes/year) 33 and between 72-95% (57-75 tonnes/year) 4,34 mineralization of injected CO2, respectively.”
    Quote in the paperNot a substantial claim2 of 3 sources checked
    • cites [33] Pogge von Strandmann, P. A. E. et al. Rapid CO2 mineralisation into calcite at the CarbFix storage site quantified using calcium isotopes. Nat. Commun. 10, 1983 (2019). source
    • cites [4] Matter, J. M. et al. Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions. Science 352, 1312–1314 (2016). source
    • cites [34] White, S. K. et al. Quantification of CO2 mineralization at the Wallula Basalt Pilot Project. Environ. Sci. Technol. 54, 14609–14616 (2020). source

  • May combine two claims.

    Premisecitation

    Reactivity hosted in thin water films has been demonstrated to alter geomechanical properties and subsurface porosity of reservoir rocks.

    “Among various important nanoscale processes affecting carbon storage reservoirs 41,42 , reactivity hosted in thin water films have been demonstrated to alter geomechanical properties 43 and subsurface porosity 44 of reservoir rocks.”
    Quote in the paperNot a substantial claim2 of 4 sources checked
    • cites [41] Bourg, I. C., Beckingham, L. E. & DePaolo, D. J. The nanoscale basis of CO2 trapping for geologic storage. Environ. Sci. Technol. 49, 10265–10284 (2015). source
    • cites [42] Jun, Y.-S., Zhang, L., Min, Y. & Li, Q. Nanoscale chemical processes affecting storage capacities and seals during geologic CO2 sequestration. Acc. Chem. Res. 50, 1521–1529 (2017). source
    • cites [43] Choens, R. C. et al. Impacts on mechanical strength of chemical reactions induced by hydrous supercritical CO2 in Boise Sandstone. Int. J. Greenh. Gas Control 95, 102982 (2020). source
    • cites [44] Rimmelé, G., Barlet-Gouédard, V. & Renard, F. Evolution of the petrophysical and mineralogical properties of two reservoir rocks under thermodynamic conditions relevant for CO2 geological storage at 3 km depth. Oil Gas. Sci. Technol. 65, 565–580 (2010). source

      The Conclusions report increased porosity in both reservoir rocks after exposure to wet supercritical CO₂ or CO₂-saturated water, supporting the part attributed to citation 44. The paper does not identify reactivity in thin water films as the demonstrated mechanism; its experiments used those two fluid-exposure conditions. (LLM, conf=0.84)

      Experimental — accuracy not yet measured

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

    Premisecitation

    Carbonate anions can catalyse the water exchange reaction around Mg2+ in the solvent-separated ion-pair state.

    “This is consistent with the prospect of synergistic effects arising from carbonate anions that can catalyse the water exchange reaction around Mg 2+ in the solvent-separated ion-pair state.131”
    Quote in the paperNot a substantial claim1 of 1 sources checked
    • cites [131] Raiteri, P., Demichelis, R. & Gale, J. D. Thermodynamically consistent force field for molecular dynamics simulations of alkaline-earth carbonates and their aqueous speciation. J. Phys. Chem. C 119, 24447–24458 (2015). source

      In “Solution Properties of Individual Ions” (page unavailable), the paper says water exchange around Mg²⁺ might be faster when Mg²⁺ is bound to carbonate, but reports no exchange during a 50 ns simulation. That possibility concerns carbonate-bound Mg²⁺, not the solvent-separated ion-pair state specified in the claim; the paper does not establish catalysis in that state. (LLM, conf=0.87)

      Experimental — accuracy not yet measured

  • May combine two claims.

    Premisecitation

    Amorphous silica formed during wollastonite carbonation in wet scCO2 is not porous and acts as a diffusion barrier, contributing to unique solute transport properties associated with thin water films.

    “Specifically, amorphous silica formed during wollastonite [CaSiO3] in wet scCO2 is not porous and was implicated as a diffusion barrier, contributing to fundamentally unique solute transport properties associated with thin water films.202”
    Quote in the paperSubstantial claim1 of 1 sources checked
    • cites [202] Min, Y., Li, Q., Voltolini, M., Kneafsey, T. & Jun, Y.-S. Wollastonite carbonation in water-bearing supercritical CO2: effects of particle size. Environ. Sci. Technol. 51, 13044–13053 (2017). source

      The section “Amorphous silica acts as a diffusion barrier for water-bearing scCO2” (page unavailable) describes the silica layer as low-porosity and says it can act as a diffusion barrier; it links the porosity difference to chemistry in thin water films. It does not say the layer is nonporous or establish fundamentally unique solute-transport properties. (LLM, conf=0.86)

      Experimental — accuracy not yet measured

  • May combine two claims.

    Findingnone given

    As shown in Figure 3.b, the required reaction time to achieve 50% conversion (t50%) varies significantly and is optimized around 180 °C and 140 bar.

    “As shown in Figure 3.b, the required reaction time to achieve 50% conversion (t50%) varies significantly and is optimized around 180 °C and 140 bar.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingnone given

    t50% in wet scCO2 at lower temperatures and pressures is relatively fast, signalling an enhanced reactivity.

    “We also note that t50% in wet scCO2 at lower temperatures and pressures is relatively fast, signalling an enhanced reactivity.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Premisecitation

    At depths relevant to geologic storage, the wet scCO2 phase is buoyant relative to H2O-rich fluids and will tend to displace formation water beneath the caprock and comprise a multiphase fluid at least for decadal time scales.

    “At depths relevant to geologic storage the wet scCO2 phase is buoyant relative to H2O-rich fluids and thus will tend to displace formation water beneath the caprock and comprise a multiphase fluid at least for decadal time scales.[37][38][39]”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites [37][38][39]

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

  • May combine two claims.

    Premisereasoning

    Surprising carbonation reactivity can occur in quasi-2D thin water film environments, including the emergence of phases not typically observed during carbonation in bulk aqueous solution, or at conditions different than expected.

    “Surprising carbonation reactivity can occur in these quasi-2D thin water film environments, including the emergence of phases not typically observed during carbonation in bulk aqueous solution, or the emergence of phases at conditions different than those expected.”
    Quote in the paperSubstantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing), S4 (based).

    Premisereasoning

    In practice, water consumption and production plays an important role, particularly in low-water CO2-rich fluids, due to the potential involvement of water cycling via hydrous transient phases in the carbonation pathway.

    “However, in practice water consumption and production plays an important role, particularly in low-water CO2-rich fluids, due to the potential involvement of water cycling via hydrous transient phases in the carbonation pathway.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Premisenone given

    In the subsurface, rocks rich in divalent metals can react with CO2, permanently sequestering it as stable metal carbonate minerals, with the CO2-H2O composition of the post-injection pore fluid acting as a primary control variable.

    “In the subsurface, rocks rich in divalent metals can react with CO2, permanently sequestering it in the form of stable metal carbonate minerals, with the CO2-H2O composition of the post-injection pore fluid acting as a primary control variable.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Premisereasoning

    The net water consumption in the reactions formulated by Equations (1-3) is zero, meaning water behaves akin to a catalyzer in the carbonation process.

    “Overall, the net water consumption in the reactions formulated by Equations (1-3) is zero, meaning water behaves akin to a catalyzer in the carbonation process.”
    Quote in the paperNot a substantial claim

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

    Premisenone given

    pH-dependent speciation reactions favor carbonic acid and carbonate in acidic and basic conditions, respectively.

    “These pH-dependent speciation reactions favor carbonic acid and carbonate in acidic and basic conditions, respectively.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Premisereasoning

    Silicic acid can polymerize over time to form an amorphous secondary passivation layer that limits reaction kinetics while producing water.

    “Over time, the silicic acid can polymerize to form an amorphous secondary passivation layer that limits the reaction kinetics while producing water, Equation (3).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Premisecitation

    Only Å-to nm-thick interfacial water films separate wet scCO2 from reactive surfaces, and they serve as the principal medium for dissolution-precipitation processes.

    “These rapid mineralization reactions are particularly significant in light of the expectation that only Å-to nmthick (single-digit nm or less) interfacial water films 38,45,50,53,54 separate wet scCO2 from reactive surfaces, and serve as the principal medium for the needed dissolution-precipitation processes.”
    Quote in the paperSubstantial claim0 of 5 sources checked
    • cites [38] Loring, J. S., Miller, Q. R. S., Thompson, C. J. & Schaef, H. T. in Science of Carbon Storage in Deep Saline Formations (eds Newell, P. & Ilgen, A. G.) 63–88 (Elsevier, 2019). source
    • cites [45] Loring, J. S. et al. In situ infrared spectroscopic study of forsterite carbonation in wet supercritical CO2. Environ. Sci. Technol. 45, 6204–6210 (2011). The first direct observation of reactive thin water film development on mineral surfaces exposed to wet scCO2. source
    • cites [50] Schaef, H. T. et al. Forsterite [Mg2SiO4)] carbonation in wet supercritical CO2: an in situ high-pressure X-ray diffraction study. Environ. Sci. Technol. 47, 174–181 (2013). source
    • cites [53] Miller, Q. R. S. et al. Insights into silicate carbonation processes in water-bearing supercritical CO2 fluids. Int. J. Greenh. Gas Control 15, 104–118 (2013). source
    • cites [54] Placencia-Gómez, E. et al. Critical water coverage during forsterite carbonation in thin water films: activating dissolution and mass transport. Environ. Sci. Technol. 54, 6888–6899 (2020). source

  • Probably not a substantial claim: may not pass S4 (based). May combine two claims.

    Premisenone given

    The structure and distribution of the thin water film controls dielectric permittivity, viscosity and, in turn, surface speciation and charge, ion speciation and solubilities, pH, ion diffusivities, and percolation pathways.

    “Key uncertainties obtained from the generally unknown structure and distribution of the thin water film, which controls dielectric permittivity, viscosity and, in turn, surface speciation and charge, ion speciation and solubilities, pH, ion diffusivities, and percolation pathways.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing), S4 (based). May combine two claims.

    Premisenone given

    At a given temperature and pressure, CO2 speciation depends strongly on pH, with carbonic acid dominant in acidic and carbonate in basic conditions.

    “At a given temperature and pressure, the speciation depends strongly on pH, with carbonic acid dominant in acidic and carbonate in basic conditions.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing), S4 (based). May combine two claims.

    Interpretationreasoning

    For forsterite carbonation, this could imply more facile Mg2+ dehydration or Mg-CO3 interfacial contact ion-pair formation in thin films, energetically akin to that of Ca2+ ions.

    “For forsterite carbonation this could imply more facile Mg 2+ dehydration or Mg-CO3 interfacial contact ion-pair formation in thin films, energetically akin to that of Ca 2+ ions.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationreasoning

    The increased hydrogen bond strength, hindered rotational degrees of freedom, and decreased self-diffusivity of adsorbed water entail a lower apparent viscosity and consequently slower reaction rates.

    “On the one hand, adsorbed water molecules exhibit increased hydrogen bond strength, 143-145 hindered rotational degrees of freedom, 145,146 and decreased selfdiffusivity [147][148][149][150][151] , which entails a lower apparent viscosity and consequently slower reaction rates.”
    Quote in the paperSubstantial claim

  • Classified as probably not a substantial claim.

    Premisecitation

    In classical nucleation theory adapted to heterogeneous pathways, nucleation preferentially occurs on existing mineral surfaces with an effective interfacial free energy γ′ = γ_lc - (γ_ls - γ_sc)/2.

    “However, in classical nucleation theory adapted to heterogeneous pathways, nucleation preferentially occurs on the existing mineral surface(s) with an effective interfacial free energy (γ′) defined as 𝛾 ′ = 𝛾 𝑙𝑐 -(𝛾 𝑙𝑠 -𝛾 𝑠𝑐 )/2, where l, c and s subscripts respectively denote liquid, crystal, and surface (step 5).133”
    Quote in the paperSubstantial claim0 of 1 sources checked
    • cites [133] Kashchiev, D. Nucleation (Butterworth-Heinemann, 2000). source

  • May combine two claims.

    Interpretationreasoning

    Because cation dehydration is an integral part of forming the cation-carbonate bonds that comprise metal carbonates, the observations can be framed in terms of relative affinities of the cations for inner-sphere waters of hydration.

    “Because cation dehydration is an integral part of forming the cation-carbonate bonds that comprise metal carbonates, one can frame these observations in terms of relative affinities of the cations for inner-sphere waters of hydration.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Premisecitation

    The crystallization process nominally proceeds by monomer addition unless the extent of supersaturation favors nucleation and self-assembly of particles, so-called particle-mediated crystallization pathways.

    “The crystallization process nominally proceeds by monomer addition unless the extent of supersaturation favors nucleation and self-assembly of particles, so-called particle-mediated crystallization pathways.134”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites [134] Yoreo, J. J. D. et al. Crystallization by particle attachment in synthetic, biogenic, and geologic environments. Science 349, aaa6760 (2015). source

  • Probably not a substantial claim: may not pass S3 (load-bearing), S4 (based). May combine two claims.

    Interpretationnone given

    A reduced dielectric constant and less effective charge screening may also contribute to the observed effects in thin water films.

    “Conceptually, a reduced dielectric constant and less effective charge screening may also contribute.”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing), S4 (based). May combine two claims.

    Interpretationnone given

    Adsorbed water nanofilms confine reactants to a smaller volume and increase the collision frequency at the mineral-H2O-CO2 interface, conceptually capable of promoting increased surface reactivity.

    “On the other hand, adsorbed water nanofilms confine reactants to a smaller volume and increase the collision frequency at the mineral-H2O-CO2 interface, conceptually capable of promoting increased surface reactivity.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Premisecitation

    Adsorbed water molecules exhibit increased hydrogen bond strength, hindered rotational degrees of freedom, and decreased self-diffusivity.

    “On the one hand, adsorbed water molecules exhibit increased hydrogen bond strength, 143-145 hindered rotational degrees of freedom, 145,146 and decreased selfdiffusivity [147][148][149][150][151] , which entails a lower apparent viscosity and consequently slower reaction rates.”
    Quote in the paperSubstantial claim0 of 5 sources checked
    • cites [143] Musat, R. et al. Finite size effects on hydrogen bonds in confined water. Angew. Chem. Int. Ed. 47, 8033–8035 (2008). source
    • cites [144] Le Caër, S. et al. Time-resolved studies of water dynamics and proton transfer at the alumina−air interface. J. Am. Chem. Soc. 129, 11720–11729 (2007). source
    • cites [145] Caër, S. L. et al. A trapped water network in nanoporous material: the role of interfaces. Phys. Chem. Chem. Phys. 13, 17658–17666 (2011). source
    • cites [146] Bonnaud, P. A., Coasne, B. & Pellenq, R. J.-M. Molecular simulation of water confined in nanoporous silica. J. Phys. Condens. Matter 22, 284110 (2010). source
    • cites [147][148][149][150][151]

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

  • May combine two claims.

    Premisecitation

    At low water coverages, complexes and limited nano-precipitates are the dominant manifestations of reactivity, whereas magnesite formation is promoted in thin water films above 1.5 ML.

    “At low water-coverages, complexes 47,48 and limited nano-precipitates 47 are the dominant manifestations of reactivity, whereas magnesite formation is promoted in the thin water film above 1.5 ML.”
    Quote in the paperSubstantial claim0 of 2 sources checked
    • cites [47] Miller, Q. R. S. et al. Surface-catalyzed oxygen exchange during mineral carbonation in nanoscale water films. J. Phys. Chem. C 123, 12871–12885 (2019). source
    • cites [48] Loring, J. S. et al. Evidence for carbonate surface complexation during forsterite carbonation in wet supercritical carbon dioxide. Langmuir 31, 7533–7543 (2015). source

  • May combine two claims.

    Premisecitation

    Bulk equilibrium thermodynamic calculations and experimental data indicate that these polymorphs may transform to magnesite above 60 °C, which involves drying-shrinkage and dissolution-precipitation solvent-mediated mechanisms.

    “Bulk equilibrium thermodynamic calculations and experimental data indicate that these polymorphs may transform to magnesite above 60 °C, 73 which involves drying-shrinkage and dissolution-precipitation solvent-mediated mechanisms. 74”
    Quote in the paperNot a substantial claim0 of 2 sources checked
    • cites [73] Chaka, A. M. & Felmy, A. R. Ab initio thermodynamic model for magnesium carbonates and hydrates. J. Phys. Chem. A 118, 7469–7488 (2014). source
    • cites [74] Hänchen, M., Prigiobbe, V., Baciocchi, R. & Mazzotti, M. Precipitation in the Mg-carbonate system — effects of temperature and CO2 pressure. Chem. Eng. Sci. 63, 1012–1028 (2008). source

  • May combine two claims.

    Interpretationreasoning

    Since CO2 is displaced from the surface, carbonic acid and bicarbonate form either with hydroxyl groups at the water-solid interface or adsorbed water molecules and catalysed by dissolved metal ions.

    “Since CO2 is displaced from the surface, carbonic acid and bicarbonate form either with hydroxyl groups at the water-solid interface (Step 2a) or adsorbed water molecules and catalysed by the dissolved metal ions (Step 2b).”
    Quote in the paperSubstantial claim
    • Rests on an assumption: CO2 is displaced from the mineral surface when wet CO2 contacts it.

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

    Premisecitation

    The importance of water-bearing CO2 for the stability and carbonation of steel, steel slag, cement, and fly ash is well established.

    “The importance of waterbearing CO2 for the stability and carbonation of steel, steel slag, cement, and fly ash is well etablished.153,239- 244”
    Quote in the paperNot a substantial claim0 of 7 sources checked
    • cites [153] Regnault, O., Lagneau, V. & Schneider, H. Experimental measurement of portlandite carbonation kinetics with supercritical CO2. Chem. Geol. 265, 113–121 (2009). source
    • cites [239] Barlet-Gouédard, V., Rimmelé, G., Porcherie, O., Quisel, N. & Desroches, J. A solution against well cement degradation under CO2 geological storage environment. Int. J. Greenh. Gas Control 3, 206–216 (2009). source
    • cites [240] Barlet-Gouédard, V., Rimmelé, G., Goffé, B. & Porcherie, O. Well technologies for CO2 geological storage: CO2-resistant cement. Oil Gas. Sci. Technol. 62, 325–334 (2007). source
    • cites [241] Hua, Y., Barker, R. & Neville, A. Comparison of corrosion behaviour for X-65 carbon steel in supercritical CO2-saturated water and water-saturated/unsaturated supercritical CO2. J. Supercrit. Fluids 97, 224–237 (2015). source
    • cites [242] Kutchko, B. G., Strazisar, B. R., Dzombak, D. A., Lowry, G. V. & Thaulow, N. Degradation of well cement by CO2 under geologic sequestration conditions. Environ. Sci. Technol. 41, 4787–4792 (2007). source
    • cites [243] Rimmelé, G., Barlet-Gouédard, V., Porcherie, O., Goffé, B. & Brunet, F. Heterogeneous porosity distribution in Portland cement exposed to CO2-rich fluids. Cem. Concr. Res. 38, 1038–1048 (2008). source
    • cites [244] Santos, R. M. et al. Accelerated mineral carbonation of stainless steel slags for CO2 storage and waste valorization: effect of process parameters on geochemical properties. Int. J. Greenh. Gas Control 17, 32–45 (2013). source

  • May combine two claims.

    Interpretationnone given

    Carbonic acid and bicarbonate deprotonate to form carbonate anions that may chemisorb on the surface to produce a metal-carbonate surface complex.

    “The carbonic acid and bicarbonate deprotonate to form carbonate anions that may chemisorb on the surface to produce a metal-carbonate surface complex (Step 2c).”
    Quote in the paperSubstantial claim

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

    Premisecitation

    The emergence of silica-rich 'leached layers' during metal silicate mineral dissolution in contact with bulk aqueous solution that can act as passivating layers is a well-known phenomenon, though debate continues regarding the deposition and polymerization mechanism.

    “The emergence of silica-rich 'leached layers' during metal silicate mineral dissolution in contact with bulk aqueous solution that can act as passivating layers is a well-known phenomenon, though debate continues regarding the deposition and polymerization mechanism.200,201”
    Quote in the paperNot a substantial claim0 of 2 sources checked
    • cites [200] Hellmann, R. et al. Nanometre-scale evidence for interfacial dissolution–reprecipitation control of silicate glass corrosion. Nat. Mater. 14, 307–311 (2015). source
    • cites [201] Hellmann, R. et al. Unifying natural and laboratory chemical weathering with interfacial dissolution–reprecipitation: a study based on the nanometer-scale chemistry of fluid–silicate interfaces. Chem. Geol. 294–295, 203–216 (2012). source

  • May combine two claims.

    Premisecitation

    Different mineral facets can have distinct dissolution rates, hydrophilicities, and silica layer development.

    “These topics are pressing, given that different mineral facets can have distinct dissolution rates, hydrophilicities, and silicalayer development.[216][217][218][219][220]”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites [216][217][218][219][220]

      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).

    Premisecitation

    The temperature history of partial wollastonite carbonation influences the reaction extent of follow-up experiments.

    “That group also deduced that the temperature history of partial wollastonite carbonation influences the reaction extent of followup experiments.203”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites [203] Min, Y. & Jun, Y.-S. Wollastonite carbonation in water-bearing supercritical CO2: effects of water saturation conditions, temperature, and pressure. Chem. Geol. 483, 239–246 (2018). source

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

    Interpretationnone given

    Laboratory studies have demonstrated facile reactivity in thin water film environments, exemplified by carbonation processes of metal silicate minerals relevant to permanent safe storage of CO2.

    “Though seemingly counterintuitive, laboratory studies have demonstrated facile reactivity in thin water film environments, here exemplified in the context of carbonation processes of metal silicate minerals relevant to permanent safe storage of CO2.”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Interpretationnone given

    Dissolved ions and ion-pairs are transported diffusively through the adsorbed water nanofilm and reach nucleation and growth sites fueling a nanofilm-mediated monomer-by-monomer addition mechanism.

    “The dissolved ions and ion-pairs are transported diffusively through the adsorbed water nanofilm (Step 5) and reach nucleation and growth sites fueling a nanofilm-mediated monomer-by-monomer addition mechanism (Step 6).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationnone given

    The deprotonation process can involve long-range proton transport to the surface that accelerates dissolution via a proton-promoted mechanism and/or ligand-enhanced dissolution leveraging carbonate anions.

    “The deportation process can involve a longrange proton transport to the surface that accelerates the dissolution process via a proton-promoted mechanism (Step 3a) and/or a ligand-enhanced dissolution (Step 3b) leveraging the produced carbonate anions in the process.”
    Quote in the paperSubstantial claim
36 of 36

  • The authors state this as an assumption.

    The water nanofilm adsorbed on forsterite has a pH of ~3-6.

    “If a pH of ~3-6 is assumed for the water nanofilm adsorbed on forsterite 60,177 , the effective energy barrier to dissolution can be estimated to fall below 36 kJ/mol.”

  • The paper relies on this without support.

    Mineral surfaces often tend to be hydrophilic.

    “Notably, because mineral surfaces often tend to be hydrophilic, H2Obearing CO2 leads to the formation of nominally Å-to nm-scale adsorbed H2O that hosts CO2 dissolution and HxCO3(2-x)- formation.”

  • The paper relies on this without support.

    The adsorbed water nanofilm is physiochemically distinct from bulk CO2-rich and H2O phases, with properties tied to surface properties and water activity of the CO2.

    “This nanofilm is physiochemically distinct from bulk CO2-rich and H2O phases, with properties intimately tied to the surface properties and the water activity of the CO2.”

  • The paper relies on this without support.

    CO2 is displaced from the mineral surface when wet CO2 contacts it.

    “Since CO2 is displaced from the surface, carbonic acid and bicarbonate form either with hydroxyl groups at the water-solid interface (Step 2a) or adsorbed water molecules and catalysed by the dissolved metal ions (Step 2b).”
4 of 4

Cites

Flagged first, then by citations

Research works printed but not linked: 6

  1. O’Connor, W. K., Dahlin, D. C., Rush, G. E., Dahlin, C. L. & Collins, W. K. Carbon dioxide sequestration by direct mineral carbonation: process mineralogy of feed and products. Min. Metall. Explor. 19, 95–101 (2002).
  2. Prasad, P. S. R. et al. Geological sequestration of carbon dioxide in Deccan basalts: preliminary laboratory study. Curr. Sci. 96, 288–291 (2009).
  3. Kolmogorov, A. N. A statistical theory for the recrystallization of metals. Izv. Akad. Nauk USSR Ser. Math. 1, 355–359 (1937).
  4. Johnson, W. & Mehl, R. Reaction kinetics in processes of nucleation and growth. Trans. Am. Inst. Min. Metall. Eng. 135, 416–442 (1939).
  5. Marini, L. Geological Sequestration of Carbon Dioxide: Thermodynamics, Kinetics, and Reaction Path Modeling (Elsevier, 2006).
  6. Wicks, D. & King, J. ARPA-E Workshop on CO2 mineralization for energy relevant mineral extraction. ARPA https://arpa-e.energy.gov/sites/default/files/TUES%201-10%20pm%20Workshop%20Kick%20off%20-%207_13_2021%20LAST%20of%20the%20morning%20-%20part%201.pdf (2021).

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Related

Authors
Abdolhosseini Qomi, M. J., Miller, Q. R. S., Zare, S., Schaef, H. T., Kaszuba, J. P., & Rosso, K. M.
Affiliations
  • Pacific Northwest National Laboratory (US)
  • University of California, Irvine (US)
  • University of Wyoming (US)
Corresponding author
Miller, Q. R. S.
ORCID
Venue
Nature Reviews Chemistry
Publisher
Springer Science and Business Media LLC
Published
2022-08-30
Volume
6
Issue
9
Pages
598-613
ISSN
2397-3358 (ISSN-L)
DOI
10.1038/s41570-022-00418-1
OpenAlex
W4293567442
Cited by
147
References
234
Citations by year
2026: 54 · 2025: 41 · 2024: 35 · 2023: 13 · 2022: 4
FWCI
2.14
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Reviews Chemistry (publishedVersion)
  • PubMed (publishedVersion)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
Funders
  • U.S. Department of Energy (DESC0022301)
  • Office of Science
  • University of California, Irvine
  • Basic Energy Sciences (DE-SC0022301)
  • Chemical Sciences, Geosciences, and Biosciences Division
  • Pacific Northwest National Laboratory
Topics
  • Physical Sciences › Environmental Science › Environmental Engineering › CO2 Sequestration and Geologic Interactions
  • Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
  • Physical Sciences › Engineering › Biomedical Engineering › Nanopore and Nanochannel Transport Studies
Keywords
CO2 mineralization, nanoconfinement, ion solvation, hydration, decarbonization

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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.

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