Cited by 50CO2 Sequestration and Geologic InteractionsCalcium Carbonate Crystallization and InhibitionCarbon dioxide utilization in catalysis

Tunable Manipulation of Mineral Carbonation Kinetics in Nanoscale Water Films via Citrate Additives

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Miller, Quin R. S., Schaef, Herbert T., Kaszuba, John P., Qiu, Lin, Bowden, Mark E., McGrail, Bernard P.·2018·Environmental Science & Technology

Abstract

We explored the influence of a model organic ligand on mineral carbonation in nanoscale interfacial water films by conducting five time-resolved in situ X-ray diffraction (XRD) experiments at 50 °C. Forsterite was exposed to water-saturated supercritical carbon dioxide (90 bar) that had been equilibrated with 0–0.5 m citrate (C 6 H 5 O 7 –3 ) solutions. The experimental results demonstrated that greater concentrations of citrate in the nanoscale interfacial water film promoted the precipitation of magnesite (MgCO 3 ) relative to nesquehonite (MgCO 3 ·3H 2 O). At the highest concentrations tested, magnesite nucleation and growth were inhibited, lowering the carbonation rate constant from 9.1 × 10 –6 to 3.6 × 10 –6 s –1 . These impacts of citrate were due to partial dehydration of Mg 2+ (aq) and the adsorption of citrate onto nuclei and magnesite surfaces. This type of information may be used to predict and tailor subsurface mineralization rates and pathways.

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  • 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”

    From Molecular-scale mechanisms of CO2 mineralization in nanoscale interfacial water films (2022) · cites this paper as [55]

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  1. [9]9. McGrail, B. P.; Schaef, H. T.; Spane, F. A.; Cliff, J. B.; Qafoku, O.; Horner, J. A.; Thompson, C. J.; Owen, A. T.; Sullivan, C. E., Field validation of supercritical CO2 reactivity with basalts. Environmental Science & Technology Letters 2017, 4, (1), 6-10.
  2. [54]54. Xu, J.; Yan, C.; Zhang, F. F.; Konishi, H.; Xu, H. F.; Teng, H. H., Testing the cation- hydration effect on the crystallization of Ca-Mg-CO3 systems. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, (44), 17750-17755.
  3. [66]66. Hopkinson, L.; Rutt, K.; Cressey, G., The transformation of nesquehonite to hydromagnesite in the system CaO-MgO-H2O-CO2: An experimental spectroscopic study. Journal of Geology 2008, 116, (4), 387-400.
  4. [69]69. Christ, C. L.; Hostetler, P. B., Studies in the system MgO-SiO2-CO2-H2O (II); the activity-product constant of magnesite. American Journal of Science 1970, 268, 439-453.

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Authors
Miller, Q. R. S., Schaef, H. T., Kaszuba, J. P., Qiu, L., Bowden, M. E., & McGrail, B. P.
Affiliations
  • University of Wyoming (US)
  • Pacific Northwest National Laboratory (US)
  • Chinese Academy of Sciences (CN)
Corresponding author
Miller, Quin R. S.
Venue
Environmental Science & Technology
Published
2018-06-06
Volume
52
Issue
12
Pages
7138-7148
ISSN
  • 0013-936X (ISSN-L)
  • 1520-5851
OpenAlex
W2806318808
Cited by
50
References
120
Citations by year
2026: 12 · 2025: 13 · 2024: 6 · 2023: 3 · 2022: 3 · 2021: 2 · 2020: 4 · 2019: 5 · 2018: 2
FWCI
1.63
Type
journal article
Language
en
Open access
Locations
  • Environmental Science & Technology (publishedVersion)
  • PubMed (publishedVersion)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
Funders
  • School of Energy Resources, University of Wyoming
  • Office of Fossil Energy
Topics
  • Physical Sciences › Environmental Science › Environmental Engineering › CO2 Sequestration and Geologic Interactions
  • Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
  • Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
Keywords
citrate, forsterite, magnesite, nesquehonite, supercritical carbon dioxide, carbon sequestration, nucleation inhibition, citrate adsorption
MeSH terms
Carbon Dioxide, Citrates, Kinetics, Minerals, Water, Citric Acid

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