Startseite Morphological approach to understanding mineral alteration and nanoparticle formation under alkaline conditions using granitic rock thin sections
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Morphological approach to understanding mineral alteration and nanoparticle formation under alkaline conditions using granitic rock thin sections

  • Eungyeong Kim , Sung Pil Hyun und Ho Young Jo ORCID logo EMAIL logo
Veröffentlicht/Copyright: 14. August 2025
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 110 Heft 8

Abstract

The cement components in deep geological disposal facilities (DGFs) for spent nuclear fuel can increase groundwater pH, potentially altering minerals within natural barriers. Mineral dissolution (biotite, quartz, plagioclase, chlorite, and K-feldspar) and secondary-phase precipitation were investigated to provide a visually integrated understanding of the multifaceted processes. This study was based on the morphological features of granitic rock thin sections exposed to alkaline aqueous solutions (initial pH: pHo 9 and 13) using atomic force microscopy (AFM), micro-X-ray fluorescence, and scanning electron microscopy/energy-dispersive X-ray spectroscopy. Batch kinetic-alteration tests were conducted for durations from 4 h to 20 daysays using solutions with different initial pH values (pHo) The minerals exhibited more pronounced changes in surface roughness and Si release at pHo 13 than at pHo 9. Furthermore, precipitates were more abundant on the mineral surfaces at pHo 9 than at pHo 13. Fe (oxy)hydroxides and Al (oxy)hydroxides prevailed as precipitates at pHo 9, whereas Ca (oxy)hydroxides dominated at pHo 13 (pH ≥ 12.8). These findings indicate that aqueous solutions were significantly involved in the formation of the secondary-phase precipitates. Interestingly, secondary phases precipitated not only on the surface of the mineral (i.e., biotite), providing constituent ions, but also on the surfaces of adjacent minerals (i.e., quartz and plagioclase). Moreover, the possibility of a multistep process involving Al precursors for nucleation of gibbsite precipitates on the surface of K-feldspar at pHo 9 and colloidal particle formation through surface modification, often overlooked in mineral research, was identified via AFM image analysis. This methodological approach using rock thin sections can provide new visual insights regarding the dissolution–precipitation processes, including nucleation reactions, under conditions closely resembling the expected environmental settings within DGFs.

Keywords: Morphological feature; granitic rock; alteration; precipitates; nanoparticles; atomic force microscope

Acknowledgments and Funding

The authors greatly appreciate Jun Young Jung at KBSI for his assistance in performing AFM analysis, and Hyeong Soo Kim and Ph.D. candidate Jeongmin Lee at Korea University for their assistance in performing optical microscopy. We also thank Moonhee Lee at Korea Science Tech Inc. for her help with μ-XRF analysis. This work was supported by the Institute for Korea Spent Nuclear Fuel (iKSNF) and Korea Foundation of Nuclear Safety (KOFONS) grant funded by the Korea government (Nuclear Safety and Security Commission, NSSC) (RS-2021-KN066110). This work was supported by the Basic Research Project of the Korea Institute of Geoscience and Mineral Resources (KIGAM), “Research on rock properties in deep environment for HLW geological disposal” (GP2020-002), funded by the Ministry of Science and ICT of Korea.

References Cited

Alekseyev, V.A. (2019) Nanoparticles and nanofluids in water-rock interactions. Geochemistry International, 57, 357–368, https://doi.org/10.1134/S0016702919040037.Suche in Google Scholar

Bagheri, M., Lothenbach, B., Shakoorioskooie, M., and Scrivener, K. (2022) Effect of different ions on dissolution rates of silica and feldspars at high pH. Cement and Concrete Research, 152, 106644, https://doi.org/10.1016/j.cemconres.2021.106644.Suche in Google Scholar

Barrón, V. and Torrent, J. (2013) Iron, manganese and aluminium oxides and oxyhydroxides. EMU Notes in Mineralogy, 14, 297–336, https://doi.org/10.1180/EMU-notes.14.9.Suche in Google Scholar

Brady, P.V. and Walther, J.V. (1990) Kinetics of quartz dissolution at low temperatures. Chemical Geology, 82, 253–264, https://doi.org/10.1016/0009-2541(90)90084-K.Suche in Google Scholar

Brandt, F., Bosbach, D., Krawczyk-Bärsch, E., Arnold, T., and Bernhard, G. (2003) Chlorite dissolution in the acid pH-range: A combined microscopic and macroscopic approach. Geochimica et Cosmochimica Acta, 67, 1451–1461, https://doi.org/10.1016/S0016-7037(02)01293-0.Suche in Google Scholar

Brantley, S.L. (2008) Kinetics of mineral dissolution. In S.L. Brantley, J. Kubici, and A. White, Eds., Kinetics of Water-Rock Interaction, p. 151–210. Springer.Suche in Google Scholar

Butt, A.R., Ejaz, S., Baron, J.C., Ikram, M., and Ali, S. (2015) CaO nanoparticles as a potential drug delivery agent for biomedical applications. Digest Journal of Nanomaterials and Biostructures, 10, 799–809.Suche in Google Scholar

Degarmo, E., Paul, E., Black, J.T., and Kohser, R.A. (2003) Materials and Processes in Manufacturing, 9th edition, 1168 p. Wiley.Suche in Google Scholar

Echeverri, J.L.M. (2014) Stable Carbon pool in natural and anthropogenic soils: mineral protection versus chemical recalcitrance. Master’s thesis, Soil Chemistry and Chemical Soil Quality, Department of Soil Quality, Wageningen University.Suche in Google Scholar

Freij, S. and Parkinson, G.M. (2005) Surface morphology and crystal growth mechanism of gibbsite in industrial Bayer liquors. Hydrometallurgy, 78, 246–255, https://doi.org/10.1016/j.hydromet.2005.04.001.Suche in Google Scholar

Gabelich, C.J., Chen, W.R., Yun, T.I., Coffey, B.M., and Suffet, I.H. (2005) The role of dissolved aluminum in silica chemistry for membrane processes. Desalination, 180, 307–319, https://doi.org/10.1016/j.desal.2005.02.009.Suche in Google Scholar

Gardner, L.R. (1972) Conditions for direct formation of gibbsite from K-feldspar-further discussion. American Mineralogist, 57, 294–300.Suche in Google Scholar

Gazzè, S.A., Stack, A.G., Ragnarsdottir, K.V., and McMaster, T.J. (2014) Chlorite topography and dissolution of the interlayer studied with atomic force microscopy. American Mineralogist, 99, 128–138, https://doi.org/10.2138/am.2014.4478.Suche in Google Scholar

Gilkes, R.J. and Suddhiprakarn, A. (1979) Biotite Alteration in Deeply Weathered Granite. I. Morphological, Mineralogical, and Chemical Properties. Clays and Clay Minerals, 27, 349–360, https://doi.org/10.1346/CCMN.1979.0270505.Suche in Google Scholar

Jolivet, J.-P., Chanéac, C., and Tronc, E. (2004) Iron oxide chemistry. From molecular clusters to extended solid networks. Chemical Communications (Cambridge), 5, 481–487. https://doi.org/10.1039/B304532N.Suche in Google Scholar

Kennedy, C.B., Scott, S.D., and Ferris, F.G. (2004) Hydrothermal phase stabilization of 2-line ferrihydrite by bacteria. Chemical Geology, 212, 269–277, https://doi.org/10.1016/j.chemgeo.2004.08.017.Suche in Google Scholar

Kim, J., Yi, K., Jeong, Y.J., and Cheong, C.S. (2011) Geochronological and Geochemical Constraints on the Petrogenesis of Mesozoic High-K Granitoids in the Central Korean Peninsula. Gondwana Research, 20, 608–620, https://doi.org/10.1016/j.gr.2010.12.005.Suche in Google Scholar

Kim, K.-W., Baek, Y.-J., Lee, K.-Y., Chung, D.-Y., and Moon, J.-K. (2016) Treatment of radioactive waste seawater by coagulation-flocculation method using ferric hydroxide and poly acrylamide. Journal of Nuclear Science and Technology, 53, 439–450, https://doi.org/10.1080/00223131.2015.1055313.Suche in Google Scholar

Kim, E., Ahn, H., Jo, H.Y., Ryu, J.-H., and Koh, Y.-K. (2017) Chlorite alteration in aqueous solutions and uranium removal by altered chlorite. Journal of Hazardous Materials, 327, 161–170, https://doi.org/10.1016/j.jhazmat.2016.12.051.Suche in Google Scholar

Kim, Y.H., Kwon, C.W., Kim, M.S., Kim, E., Kim, T., Kim, H.-C., Nahm, W.-H., Park, I., Suk, H., Song, W.-K., and others. (2021) Research on rock properties in deep environment for HLW geological disposal. Volume GP2020–002, Korea Institute of Geoscience and Mineral Resources.Suche in Google Scholar

Knauss, K.G. and Wolery, T.J. (1986) Dependence of albite dissolution kinetics on pH and time at 25 °C and 70 °C. Geochimica et Cosmochimica Acta, 50, 2481–2497, https://doi.org/10.1016/0016-7037(86)90031-1.Suche in Google Scholar

Krawczyk-Bärsch, E., Arnold, T., Reuther, H., Brandt, F., Bosbach, D., and Bernhard, G. (2004) Formation of secondary Fe-oxyhydroxide phases during the dissolution of chlorite – Effects on uranium sorption. Applied Geochemistry, 19, 1403–1412, https://doi.org/10.1016/j.apgeochem.2004.01.017.Suche in Google Scholar

Läuchli, A. and Grattan, S.R. (2012) Soil pH extremes. Plant stress physiology, 194–209, https://doi.org/10.1079/9781845939953.0194.Suche in Google Scholar

Li, J. and Deepak, F.L. (2022) In situ kinetic observations on crystal nucleation and growth. Chemical Reviews, 122, 16911–16982, https://doi.org/10.1021/acs.chemrev.1c01067.Suche in Google Scholar

Lowson, R.T., Comarmond, M.-C., Rajaratnam, G., and Brown, P.L. (2005) The kinetics of the dissolution of chlorite as a function of pH and at 25 °C. Geochimica et Cosmochimica Acta, 69, 1687–1699, https://doi.org/10.1016/j.gca.2004.09.028.Suche in Google Scholar

Malmström, M. and Banwart, S. (1997) Biotite dissolution at 25 °C: The pH dependence of dissolution rate and stoichiometry. Geochimica et Cosmochimica Acta, 61, 2779–2799, https://doi.org/10.1016/S0016-7037(97)00093-8.Suche in Google Scholar

Malmström, M., Banwart, S., Lewenhagen, J., Duro, L., and Bruno, J. (1996) The dissolution of biotite and chlorite at 25 °C in the near-neutral pH region. Journal of Contaminant Hydrology, 21, 201–213, https://doi.org/10.1016/0169-7722(95)00047-X.Suche in Google Scholar

McMaster, T.J., Smits, M.M., Haward, S.J., Leake, J.R., Banwart, S., and Ragnarsdottir, K.V. (2008) High-resolution imaging of biotite dissolution and measurement of activation energy. Mineralogical Magazine, 72, 115–120, https://doi.org/10.1180/minmag.2008.072.1.115.Suche in Google Scholar

Nguyen, T.S. (2018) Thermo-hydro-mechanical-chemical processes in geological disposal of radioactive waste–an example of regulatory research. Advances in Geo-Energy Research, 2, 173–189, https://doi.org/10.26804/ager.2018.02.06.Suche in Google Scholar

Notini, L., ThomasArrigo, L.K., Kaegi, R., and Kretzschmar, R. (2022) Coexisting Goethite Promotes Fe(II)-Catalyzed Transformation of Ferrihydrite to Goethite. Environmental Science & Technology, 56, 12723–12733, https://doi.org/10.1021/acs.est.2c03925.Suche in Google Scholar

Rufe, E. and Hochella, M.F. Jr. (1999) Quantitative assessment of reactive surface area of phlogopite during acid dissolution. Science, 285, 874–876, https://doi.org/10.1126/science.285.5429.874.Suche in Google Scholar

Samson, S.D., Nagy, K.L., and Cotton, W.B. III. (2005) Transient and quasi-steady-state dissolution of biotite at 22–25 °C in high pH, sodium, nitrate, and aluminate solutions. Geochimica et Cosmochimica Acta, 69, 399–413, https://doi.org/10.1016/j.gca.2004.07.005.Suche in Google Scholar

Sauter, A., Roosen-Runge, F., Zhang, F., Lotze, G., Feoktystov, A., Jacobs, R.M.J., and Schreiber, F. (2015) On the question of two-step nucleation in protein crystallization. Faraday Discussions, 179, 41–58, https://doi.org/10.1039/C4FD00225C.Suche in Google Scholar

Schaefer, M.V., Handler, R.M., and Scherer, M.M. (2017) Fe(II) reduction of pyrolusite (β-MnO2) and secondary mineral evolution. Geochemical Transactions, 18, 7, https://doi.org/10.1186/s12932-017-0045-0.Suche in Google Scholar

Siretanu, I., Ebeling, D., Andersson, M.P., Stipp, S.L.S., Philipse, A., Stuart, M.C., van den Ende, D., and Mugele, F. (2014) Direct observation of ionic structure at solid-liquid interfaces: A deep look into the Stern Layer. Scientific Reports, 4, 4956, https://doi.org/10.1038/srep04956.Suche in Google Scholar

Smith, M.M., Wolery, T.J., and Carroll, S.A. (2013) Kinetics of chlorite dissolution at elevated temperatures and CO2 conditions. Chemical Geology, 347, 1–8, https://doi.org/10.1016/j.chemgeo.2013.02.017.Suche in Google Scholar

Sun, Z., Chen, Y.-G., and Ye, W.-M. (2022) A systematic review of bentonite/concrete interaction system in HLW disposal repositories: Theoretical, experimental and geochemical modelling analysis. Construction & Building Materials, 353, 129075, https://doi.org/10.1016/j.conbuildmat.2022.129075.Suche in Google Scholar

Supattarasakda, K., Petcharoen, K., Permpool, T., Sirivat, A., and Lerdwijitjarud, W. (2013) Control of hematite nanoparticle size and shape by the chemical precipitation method. Powder Technology, 249, 353–359, https://doi.org/10.1016/j.powtec.2013.08.042.Suche in Google Scholar

Tabares, J., Ortega, I.M., Bahena, J.L.R., López, A.A.S., Pérez, D.V., and Valdivieso, A.L. (2006) Surface Properties and Floatability of Molybdenite. Proceeding of the 2006 China-Mexico Workshop on Minerals Particle Technology, p. 115–124.Suche in Google Scholar

Teng, H.H., Fenter, P., Cheng, L., and Sturchio, N.C. (2001) Resolving orthoclase dissolution processes with atomic force microscopy and X-ray reflectivity. Geochimica et Cosmochimica Acta, 65, 3459–3474, https://doi.org/10.1016/S0016-7037(01)00665-2.Suche in Google Scholar

Tian, X., He, X., Song, D., Li, Z., Khan, M., Liu, H., and Qiu, L. (2022) AFM characterization of surface mechanical and electrical properties of some common rocks. International Journal of Mining Science and Technology, 32, 435–445, https://doi.org/10.1016/j.ijmst.2021.12.008.Suche in Google Scholar

Van Driessche, A.E.S., Kellermeier, M., Benning, L.G., and Gevauer, D. (2016) New perspectives on mineral nucleation and growth: from solution precursors to solid materials, 380 p. Springer.Suche in Google Scholar

Wang, L., Putnis, C.V., Ruiz-Agudo, E., Hövelmann, J., and Putnis, A. (2015) In situ imaging of interfacial precipitation of phosphate on Goethite. Environmental Science & Technology, 49, 4184–4192, https://doi.org/10.1021/acs.est.5b00312.Suche in Google Scholar

Wang, S., Zhang, X., Graham, T.R., Zhang, H., Pearce, C.I., Wang, Z., Clark, S.B., Jiang, W., and Rosso, K.M. (2020) Two-step route to size and shape controlled gibbsite nanoplates and the crystal growth mechanism. CrystEngComm, 22, 2555–2565, https://doi.org/10.1039/D0CE00114G.Suche in Google Scholar

White, A.F. and Brantley, S.L. (1995) Chemical weathering rates of silicate minerals: An overview. Reviews in Mineralogy and Geochemistry, 31, 1–22.Suche in Google Scholar

Wu, X., Lee, B., and Jun, Y.-S. (2020) Interfacial and activation energies of environmentally abundant heterogeneously nucleated iron (III) (hydr)oxide on quartz. Environmental Science & Technology, 54, 12119–12129, https://doi.org/10.1021/acs.est.0c03160.Suche in Google Scholar

Xiao, F., Zhang, B., and Lee, C. (2008) Effects of low temperature on aluminum(III) hydrolysis: Theoretical and experimental studies. Journal of Environmental Sciences (China), 20, 907–914, https://doi.org/10.1016/S1001-0742(08)62185-3.Suche in Google Scholar

Xie, W., Guo, Z., Gao, F., Gao, Q., Wang, D., Liaw, B.-S., Cai, Q., Sun, X., Wang, X., and Zhao, L. (2018) Shape-, size- and structure-controlled synthesis and biocompatibility of iron oxide nanoparticles for magnetic theranostics. Theranostics, 8, 3284–3307, https://doi.org/10.7150/thno.25220.Suche in Google Scholar

Xu, C.-Y., Deng, K.-Y., Li, J.-Y., and Xu, R.-K. (2015) Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles. Journal of Nanoparticle Research, 17, 394, https://doi.org/10.1007/s11051-015-3198-8.Suche in Google Scholar

Yokomizo, K. and Kosaka, K. (2008) Observation of Micro-pores in Granites by Atomic Force Microscope (AFM). Proceedings of the Institute of Natural Sciences, College of Humanities and Sciences, Nihon University 43, 107–119.Suche in Google Scholar

Yuan, G., Cao, Y., Schulz, H.-M., Hao, F., Gluyas, J., Liu, K., Yang, T., Wang, Y., Xi, K., and Li, F. (2019) A review of feldspar alteration and its geological significance in sedimentary basins: From shallow aquifers to deep hydrocarbon reservoirs. Earth-Science Reviews, 191, 114–140, https://doi.org/10.1016/j.earscirev.2019.02.004.Suche in Google Scholar

Zazzi, Å., Jakobsson, A.-M., and Wold, S. (2012) Ni(II) sorption on natural chlorite. Applied Geochemistry, 27, 1189–1193, https://doi.org/10.1016/j.apgeochem.2012.03.001.Suche in Google Scholar
Received: 2023-11-25
Accepted: 2024-12-05
Published Online: 2025-08-14
Published in Print: 2025-08-26

© 2025 Mineralogical Society of America

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https://doi.org/10.2138/am-2024-9261
Schlagwörter für diesen Artikel
Morphological feature; granitic rock; alteration; precipitates; nanoparticles; atomic force microscope

Artikel in diesem Heft

  1. Hematite (U-Th)/He thermochronometry unveils unique exhumation history: An example from the Dexing porphyry copper deposit, Southern China
  2. Viscosity measurements of selected lunar regolith simulants
  3. Formation of nano-CdS solid solution: A mechanism for Cd enrichment in sphalerite
  4. Identification of the nature of recycled carbonates in the mantle: Insights from the Mo-Mg isotopic pair
  5. Discriminating ionic mobility between diffusivity and electrical conductivity experiments on Earth’s silicate materials
  6. Morphological approach to understanding mineral alteration and nanoparticle formation under alkaline conditions using granitic rock thin sections
  7. Identification of hydroandradite in CM carbonaceous chondrites: Aproduct of calc-silicate alteration on C-complex asteroids
  8. Growth and crystallographic features of interpenetrant twins in natural diamonds
  9. Determination of the oxidation state of iron in calcic pyroxene using the electron microprobe flank method
  10. Formation mechanism of boehmite and diaspore in karstic bauxites: Trace element geochemistry in source materials using a large sample geochemical dataset and a random forest model
  11. High-temperature Raman spectroscopy of K2Ca(CO3)2 bütschliite and Na2Ca2(CO3)3 shortite
  12. Effects of high-temperature annealing and low-temperature metamictization on Archean zircon: Constraints from U-Pb isotopes, trace elements, and Raman dating
  13. Nanoscale insights into weathering of Ti-bearing minerals and heterogeneous crystal growth mechanisms of nano Ti oxides in altered volcanic ash
  14. High-pressure single-crystal X-ray diffraction and Raman spectroscopy of boltwoodite, K0.63Na0.37[(UO2)(SiO3OH)](H2O)1.5
  15. Nanoscale characterization of chrysocolla, black chrysocolla, and pseudomalachite from supergene copper deposits of Atacama Desert in northern Chile
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