Tunable Manipulation of Mineral Carbonation Kinetics in Nanoscale Water Films via Citrate Additives
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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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Flagged first, then by citations
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Cited by
Sorted by citations
Quantification of CO2 Mineralization at the Wallula Basalt Pilot Project
White, S. K., Spane, F. A., Schaef, H. T., Miller, Q. R. S., White, M. D., Horner, J. A., & McGrail, B. P. (2020) · Environmental Science & Technology · doi:10.1021/acs.est.0c05142 · Cited by 247 · see citing works
Self-citationMolecular-scale mechanisms of CO2 mineralization in nanoscale interfacial water films
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 · Cited by 147 · see citing works
Self-citationMiller, Q. R. S., Schaef, H. T., Kaszuba, J. P., Gadikota, G., McGrail, B. P., & Rosso, K. M. (2019) · Environmental Science & Technology Letters · doi:10.1021/acs.estlett.9b00301 · Cited by 98 · see citing works
Self-citationPlacencia-Gómez, E., Kerisit, S. N., Mehta, H. S., Qafoku, O., Thompson, C. J., Graham, T. R., Ilton, E. S., & Loring, J. S. (2020) · Environmental Science & Technology · doi:10.1021/acs.est.0c00897 · Cited by 57 · see citing works
Anomalously low activation energy of nanoconfined MgCO <sub>3</sub> precipitation
Miller, Q. R. S., Kaszuba, J. P., Schaef, H. T., Bowden, M. E., McGrail, B. P., & Rosso, K. M. (2019) · Chemical Communications · doi:10.1039/c9cc01337g · Cited by 49 · see citing works
Self-citationSurface-Catalyzed Oxygen Exchange during Mineral Carbonation in Nanoscale Water Films
Miller, Q. R. S., Dixon, D. A., Burton, S. D., Walter, E. D., Hoyt, D. W., McNeill, A. S., Moon, J. D., Thanthiriwatte, K. S., Ilton, E. S., Qafoku, O., et al. (2019) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.9b02215 · Cited by 42 · see citing works
Self-citationMiller, Q. R. S., Kaszuba, J. P., Kerisit, S. N., Schaef, H. T., Bowden, M. E., McGrail, B. P., & Rosso, K. M. (2020) · Environmental Science: Nano · doi:10.1039/c9en01382b · Cited by 41 · see citing works
Self-citationSendula, E., Lamadrid, H. M., Rimstidt, J. D., Steele-MacInnis, M., Sublett, D. M., Aradi, L. E., Szabó, C., Caddick, M. J., Zajacz, Z., & Bodnar, R. J. (2021) · Frontiers in Climate · doi:10.3389/fclim.2021.722447 · Cited by 26 · see citing works
Molecular Intermediate in the Directed Formation of a Zeolitic Metal–Organic Framework
Sinnwell, M. A., Miller, Q. R. S., Palys, L., Barpaga, D., Liu, L., Bowden, M. E., Han, Y., Ghose, S., Sushko, M. L., Schaef, H. T., et al. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c07862 · Cited by 21 · see citing works
Self-citationWater Structure Controls Carbonic Acid Formation in Adsorbed Water Films
Miller, Q. R. S., Ilton, E. S., Qafoku, O., Dixon, D. A., Vasiliu, M., Thompson, C. J., Schaef, H. T., Rosso, K. M., & Loring, J. S. (2018) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.8b02162 · Cited by 19 · see citing works
Self-citationLi, G., Naim, Z., Gibert, L., Stuut, J., Waajen, A. C., Jimenez‐Moreno, G., & Sánchez‐Román, M. (2026) · The Depositional Record · doi:10.1002/dep2.70058 · Cited by 2 · see citing works
- 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
- Publisher
- American Chemical Society (ACS)
- Published
- 2018-06-06
- Volume
- 52
- Issue
- 12
- Pages
- 7138-7148
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- OpenAlex
- W2806318808
- Semantic Scholar
- 0774360eb2b6ef26c74deed28ca5332d60f44b39
- 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
- green
- www.osti.gov
- 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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