Articles | Volume 38, issue 2
https://doi.org/10.5194/ejm-38-197-2026
© Author(s) 2026. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/ejm-38-197-2026
© Author(s) 2026. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Selective uptake of rare earth elements and other cations in sector-zoned natural calcite as analogues for trivalent actinide behavior
Ferdinand Baumeister
CORRESPONDING AUTHOR
Technische Universität Berlin, Department of Applied Geochemistry, 10587 Berlin, Germany
Martin Kutzschbach
Technische Universität Berlin, Department of Applied Geochemistry, 10587 Berlin, Germany
Martina Klinkenberg
Forschungszentrum Jülich GmbH, Institute of Fusion Energy and Nuclear Waste Management (IFN), Nuclear Waste Management (IFN-2), 52425 Jülich, Germany
Felix Brandt
Forschungszentrum Jülich GmbH, Institute of Fusion Energy and Nuclear Waste Management (IFN), Nuclear Waste Management (IFN-2), 52425 Jülich, Germany
Thomas Neumann
Technische Universität Berlin, Department of Applied Geochemistry, 10587 Berlin, Germany
Related authors
No articles found.
Ferdinand J. Hampl, Ferry Schiperski, Christopher Schwerdhelm, Nicole Stroncik, Casey Bryce, Friedhelm von
Blanckenburg, and Thomas Neumann
Earth Surf. Dynam., 11, 511–528, https://doi.org/10.5194/esurf-11-511-2023, https://doi.org/10.5194/esurf-11-511-2023, 2023
Short summary
Short summary
We investigated the mineral content and geochemical composition of the upper 6 m of regolith, formed by weathering of granitic rocks in Mediterranean and humid climate zones. We found that the development of the upper regolith in the Mediterranean climate is controlled by secondary minerals which cause fracturing and thus facilitate fluid infiltration to depth. The upper regolith in the humid climate is controlled by secondary minerals that cause a reduction of fluid infiltration to depth.
Felix Brandt, Martina Klinkenberg, Sébastien Caes, Jenna Poonoosamy, Wouter Van Renterghem, Juri Barthel, Karel Lemmens, Dirk Bosbach, and Karine Ferrand
Saf. Nucl. Waste Disposal, 1, 143–144, https://doi.org/10.5194/sand-1-143-2021, https://doi.org/10.5194/sand-1-143-2021, 2021
Philip Kegler, Martina Klinkenberg, Felix Brandt, Guido Deissmann, and Dirk Bosbach
Saf. Nucl. Waste Disposal, 1, 91–93, https://doi.org/10.5194/sand-1-91-2021, https://doi.org/10.5194/sand-1-91-2021, 2021
Jenna Poonoosamy, Martina Klinkenberg, Mara Lönartz, Yuankai Yang, Guido Deissmann, Felix Brandt, and Dirk Bosbach
Saf. Nucl. Waste Disposal, 1, 105–107, https://doi.org/10.5194/sand-1-105-2021, https://doi.org/10.5194/sand-1-105-2021, 2021
Cited articles
Apted, M. J. and Ahn, J.: Repository 101: Multiple-barrier geological repository design and isolation strategies for safe disposal of radioactive materials, Woodhead Publ. Series Energy, 2017, 3–26, https://doi.org/10.1016/B978-0-08-100642-9.00001-3, 2017.
Baatartsogt, B., Schwinn, G., Wagner, T., Taubald, H., Beitter, T., and Markl, G.: Contrasting paleofluid systems in the continental basement: a fluid inclusion and stable isotope study of hydrothermal vein mineralization, Schwarzwald district, Germany, Geofluids, 7, 123–147, https://doi.org/10.1111/j.1468-8123.2007.00169.x, 2007.
Barker, S. L. L. and Cox, S. F.: Oscillatory zoning and trace element incorporation in hydrothermal minerals: insights from calcite growth experiments, Geofluids, 11, 48–56, https://doi.org/10.1111/j.1468-8123.2010.00305.x, 2011.
Bau, M.: Rare-earth element mobility during hydrothermal and metamorphic fluid-rock interaction and the significance of the oxidation state of europium, Chem. Geol., 93, 219–230, https://doi.org/10.1016/0009-2541(91)90115-8, 1991.
Birkholzer, J., Houseworth, J., and Tsang, C. F.: Geologic disposal of high-level radioactive waste: status, key issues, and trends, Annu. Rev. Environ. Resour., 37, 79–106, https://doi.org/10.1146/annurev-environ-090611-143314, 2012.
Bruno, J. and Sandino, A.: Radionuclide co-precipitation, SKB Tech. Rep., 87-23, 1987.
Bruno, M., Massaro, F. R., Pastero, L., Costa, E., Rubbo, M., Prencipe, M., and Aquilano, D.: New estimates of the free energy of calcite/water interfaces for evaluating the equilibrium shape and nucleation mechanisms, Cryst. Growth Des., 13, 1170–1179, https://doi.org/10.1021/cg3015817, 2013.
Burgos-Cara, A., Putnis, C. V., Rodriguez-Navarro, C., and Ruiz-Agudo, E.: Hydration effects on the stability of calcium carbonate pre-nucleation species, Minerals, 7, 126, https://doi.org/10.3390/min7070126, 2017.
Burisch, M., Walter, B. F., Gerdes, A., Lanz, M., and Markl, G.: Late-stage anhydrite-gypsum-siderite-dolomite-calcite assemblages record the transition from a deep to a shallow hydrothermal system in the Schwarzwald mining district, SW Germany, Geochim. Cosmochim. Ac., 223, 259–278, https://doi.org/10.1016/j.gca.2017.12.002, 2018.
Curti, E.: Coprecipitation of radionuclides with calcite: estimation of partition coefficients based on a review of laboratory investigations and geochemical data, Appl. Geochem., 14, 433–445, https://doi.org/10.1016/S0883-2927(98)00065-1, 1999.
Di, J. and Ding, X.: Complexation of REE in hydrothermal fluids and its significance on REE mineralization, Minerals, 14, 531, https://doi.org/10.3390/min14060531, 2024.
Drake, H., Mathurin, F. A., Zack, T., and Schäfer, T.: Incorporation of trace elements into calcite precipitated from deep anoxic groundwater in fractured granitoid rocks, Procedia Earth Planet. Sci., 17, 841–844, https://doi.org/10.1016/j.proeps.2017.01.056, 2017.
Dziadkowiec, J., Ban, M., Javadi, S., Jamtveit, B., and Royne, A.: Ca2+ ions decrease adhesion between two (104) calcite surfaces as probed by atomic force microscopy, ACS Earth Space Chem., 5, 2827–2838, https://doi.org/10.1021/acsearthspacechem.1c00220, 2021.
Elzinga, E. J., Reeder, R. J., Withers, S. H., Peale, R. E., Manson, R. A., Beck, K. M., and Hess, W. P.: EXAFS study of rare-earth element coordination in calcite, Geochim. Cosmochim. Ac., 66, 2875–2885, https://doi.org/10.1016/S0016-7037(02)00888-8, 2002.
Fenter, P. and Sturchio, N. C.: Mineral-water interfacial structures revealed by synchrotron X-ray scattering, Prog. Surf. Sci., 77, 171–258, https://doi.org/10.1016/j.progsurf.2004.12.001, 2004.
Fenter, P., Geissbühler, P., DiMasi, E., Srajer, G., Sorensen, L. B., and Sturchio, N. C.: Surface speciation of calcite observed in situ by high-resolution X-ray reflectivity, Geochim. Cosmochim. Ac., 64, 1221–1228, https://doi.org/10.1016/S0016-7037(99)00403-2, 2000.
Gabitov, R. I., Sadekov, A., and Migdisov, A.: REE incorporation into calcite individual crystals as one time spike addition, Minerals, 7, 204, https://doi.org/10.3390/min7110204, 2017.
Gabitov, R. I., Sadekov, A., Dyer, J., Perez-Huerta, A., Xu, H., and Migdisov, A.: Sectoral and growth rate control on elemental uptake by individual calcite crystals, Chem. Geol., 585, 120589, https://doi.org/10.1016/j.chemgeo.2021.120589, 2021.
Geyer, O. F., Gwinner, M. P., Geyer, M., Nitsch, E., and Simon, T.: Geologie von Baden-Württemberg, Schweizerbart, Stuttgart, 627 pp., ISBN 978-3-510-65267-9, 2011.
Hann, H. P.: Tektonik und Petrologie des Südschwarzwälder Kristallins im Gebiet des unteren Wehratals, Neues Jahrb. Geol. Paläontol. Abh., 240, 121–151, https://doi.org/10.1127/njgpa/240/2006/121, 2006.
Heberling, F., Trainor, T. P., Lützenkirchen, J., Eng, P., Denecke, M. A., and Bosbach, D.: Structure and reactivity of the calcite-water interface, J. Colloid Interf. Sci., 354, 843–857, https://doi.org/10.1016/j.jcis.2010.10.047, 2011.
Heberling, F., Bosbach, D., Eckhardt, J. D., Fischer, U., Glowacky, J., Haist, M., Kramar, U., Loos, S., Müller, H. S., Neumann, T., Pust, C., Schäfer, T., Stelling, J., Ukrainczyk, M., Vinograd, V., Vucak, M., and Winkler, B.: Reactivity of the calcite-water interface, from molecular scale processes to geochemical engineering, Appl. Geochem., 45, 158–190, https://doi.org/10.1016/j.apgeochem.2014.03.006, 2014.
Heller, A., Barkleit, A., Foerstendorf, H., Tsushima, S., Heim, K., and Bernhard, G.: Curium(III) citrate speciation in biological systems: a europium(III)-assisted spectroscopic and quantum chemical study, Dalton Trans., 41, 13969, https://doi.org/10.1039/c2dt31480k, 2012.
Heller, A., Senwitz, C., Foerstendorf, H., Tsushima, S., Holtmann, L., Drobot, B., and Kretzschmar, J.: Europium(III) meets etidronic acid (HEDP): a coordination study combining spectroscopic, spectrometric, and quantum chemical methods, Molecules, 28, 4469, https://doi.org/10.3390/molecules28114469, 2023.
Jensen, M. P. and Bond, A. H.: Comparison of covalency in the complexes of trivalent actinide and lanthanide cations, J. Am. Chem. Soc., 124, 9870–9877, https://doi.org/10.1021/ja0178620, 2002.
Kalt, A., Altherr, R., and Hanel, M.: Contrasting P–T conditions recorded in ultramafic high-pressure rocks from the Variscan Schwarzwald (F.R.G.), Contrib. Mineral. Petrol., 121, 45–60, https://doi.org/10.1007/s004100050089, 1995.
Kalt, A., Altherr, R., and Hanel, M.: The Variscan basement of the Schwarzwald, Ber. Dtsch. Mineral. Ges., 1–43, https://www.researchgate.net/publication/269092883_The_Variscan_Basement_of_the_Schwarzwald (last access: 17 April 2026), 2000.
Kepp, K. P.: Thermochemically consistent free energies of hydration for di- and trivalent metal ions, J. Phys. Chem. A, 122, 7464–7471, https://doi.org/10.1021/acs.jpca.8b06674, 2018.
Kim, J. S., Kwon, S. K., Sanchez, M., and Cho, G. C.: Geological storage of high-level nuclear waste, KSCE J. Civ. Eng., 15, 721–737, https://doi.org/10.1007/s12205-011-0012-8, 2011.
Krauskopf, K. B.: Thorium and rare-earth metals as analogs for actinide elements, Chem. Geol., 55, 323–335, https://doi.org/10.1016/0009-2541(86)90033-1, 1986.
Kurniawan, T. A., Othman, M. H. D., Singh, D., Avtar, R., Hwang, G. H., Setiadi, T., and Lo, W.-H.: Technological solutions for long-term storage of partially used nuclear waste: a critical review, Ann. Nucl. Energy, 166, 108736, https://doi.org/10.1016/j.anucene.2021.108736, 2021.
Kusturica, A., van Loon, N., Drake, H., and Schäfer, T.: LA-ICP-MS analysis of trace and rare-earth element distribution in calcite fracture fillings from Forsmark, Simpevarp and Laxemar (Sweden), Environ. Earth Sci., 81, 371, https://doi.org/10.1007/s12665-022-10462-1, 2022.
Lakshtanov, L. Z. and Stipp, S. L. S.: Experimental study of europium(III) coprecipitation with calcite, Geochim. Cosmochim. Ac., 68, 819–827, https://doi.org/10.1016/j.gca.2003.07.010, 2004.
Louvel, M., Etschmann, B., Guan, Q., Testemale, D., and Brugger, J.: Carbonate complexation enhances hydrothermal transport of rare earth elements in alkaline fluids, Nat. Commun., 13, 1456, https://doi.org/10.1038/s41467-022-28943-z, 2022.
Marques Fernandes, M., Schmidt, M., Stumpf, T., Walther, C., Bosbach, D., Klenze, R., and Fanghänel, T.: Site-selective time-resolved laser fluorescence spectroscopy of Eu3+ in calcite, J. Colloid Interf. Sci., 321, 323–331, https://doi.org/10.1016/j.jcis.2008.01.017, 2008.
Metz, R., Richter, M., and Schürenberg, H.: Die Blei-Zink-Erzgänge des Schwarzwaldes, Amt für Bodenforschung, Beihefte zum Geologischen Jahrbuch, Stuttgart, Beiheft 29, 277 pp., ES184032900, http://www.schweizerbart.de//publications/detail/artno/184032900/Beih_29_z_Geol_Jahrbuch_vergriffen (last access: 17 April 2026), 1957.
Möller, P. and De Lucia, M.: Incorporation of rare earths and yttrium in calcite: a critical re-evaluation, Aquat. Geochem., 26, 89–117, https://doi.org/10.1007/s10498-020-09369-9, 2020.
Morgan, J. W. and Wandless, G. A.: Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control, Geochim. Cosmochim. Ac., 44, 973–980, https://doi.org/10.1016/0016-7037(80)90286-0, 1980.
Nedel, S., Didieriksen, K., Christiansen, B. C., Bovet, N., and Stipp, S. L. S.: Uptake and release of cerium during Fe-oxide formation and transformation in Fe(II) solutions, Environ. Sci. Technol., 44, 4493–4498, https://doi.org/10.1021/es9031503, 2010.
Olszewska, A., Miskiewicz, A., Zakrzeska-Koltuniewicz, G., Lankof, L., and Pajak, L.: Multi-barrier system against migration of radionuclides from radioactive waste repository, Nukleonika, 60, 557–563, https://doi.org/10.1515/nuka-2015-0103, 2015.
Paquette, J. and Reeder, R. J.: Relationship between surface structure, growth mechanism, and trace element incorporation in calcite, Geochim. Cosmochim. Ac., 59, 735–749, https://doi.org/10.1016/0016-7037(95)00004-J, 1995.
Perry, E. P.: Rare earth element signatures in hydrothermal calcite: insights from numerical modeling, experimental geochemistry and mineral deposits in New Mexico, PhD thesis, Colorado School of Mines, 13857310, https://doi.org/10.1155/2018/5382480, 2019.
Pflug, R.: Bau und Entwicklung des Oberrheingrabens, Wiss. Buchges., Darmstadt, 145 pp., ISBN 3-534-07186-7, 1982.
Reeder, R. J. and Paquette, J.: Sector zoning in natural and synthetic calcites, Sediment. Geol., 65, 239–247, https://doi.org/10.1016/0037-0738(89)90026-2, 1989.
Reeder, R. J.: Interaction of divalent cobalt, zinc, cadmium, and barium with the calcite surface during layer growth, Geochim. Cosmochim. Ac., 60, 1543–1552, https://doi.org/10.1016/0016-7037(96)00034-8, 1996.
Schwinn, G. and Markl, G.: REE systematics in hydrothermal fluorite, Chem. Geol., 216, 225–248, https://doi.org/10.1016/j.chemgeo.2004.11.012, 2005.
Shannon, R. D.: Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr. A, 32, 751–767, https://doi.org/10.1107/S0567739476001551, 1976.
Staude, S., Mordhorst, T., Nau, S., Pfaff, K., Brügmann, G., Jacob, D. E., and Markl, G.: Hydrothermal carbonates of the Schwarzwald ore district, southwestern Germany: carbon source and conditions of formation using δ18O, δ13C, 87Sr/86Sr, and fluid inclusions, Can. Mineral., 50, 1401–1434, https://doi.org/10.3749/canmin.50.5.1401, 2012.
Stipp, S. L. S., Christensen, J. T., Lakshtanov, L. Z., Baker, J. A., and Waight, T. E.: Rare earth element (REE) incorporation in natural calcite: upper limits for actinide uptake in a secondary phase, Radiochim. Acta, 94, 523–528, https://doi.org/10.1524/ract.2006.94.9-11.523, 2009.
Subías, I. and Fernández-Nieto, C.: Hydrothermal events in the Valle de Tena (Spanish Western Pyrenees) as evidenced by fluid inclusions and trace-element distribution from fluorite deposits, Chem. Geol., 124, 267–282, https://doi.org/10.1016/0009-2541(95)00060-Y, 1995.
Voigt, M., Mavromatis, V., and Oelkers, E. H.: The experimental determination of REE partition coefficients in the water-calcite system, Chem. Geol., 462, 30–43, https://doi.org/10.1016/j.chemgeo.2017.04.024, 2017.
Walter, B. F., Immenhauser, A., Geske, A., and Markl, G.: Exploration of hydrothermal carbonate magnesium isotope signatures as tracers for continental fluid aquifers, Schwarzwald mining district, SW Germany, Chem. Geol., 400, 87–105, https://doi.org/10.1016/j.chemgeo.2015.02.009, 2015.
Warmada, W., Lehmann, B., Simandjuntak, M., and Hemes, H. S.: Fluid inclusion, rare-earth element and stable isotope study of carbonate minerals from the Pongkor epithermal gold-silver deposit, West Java, Indonesia, Resour. Geol., 57, 124–135, https://doi.org/10.1111/j.1751-3928.2007.000012.x, 2007.
Werner, W. and Dennert, V.: Lagerstätten und Bergbau im Schwarzwald, Landesamt Geol. Rohst. Bergbau Baden-Württemberg, ISBN-10 3000146369, 2004.
Xue, Y., Sun, D., Wang, L., and Xu, Y.: A double-layered model for near-field temperature in a nuclear waste repository, Prog. Nucl. Energy, 133, 103646, https://doi.org/10.1016/j.pnucene.2021.103646, 2021.
Zhao, H. G., Shao, H., Kunz, H., Wang, J., Su, R., and Liu, Y. M.: Numerical analysis of thermal process in the near field around vertical disposal of high-level radioactive waste, J. Rock Mech. Geotech. Eng., 6, 55–60, https://doi.org/10.1016/j.jrmge.2013.09.004, 2014.
Zheng, J., Wen, W., Ge, Y., Zhou, G., Zhang, Y., Yan, W., Jiang, H., Zhang, Z., and Xi, A.: U–Pb dating of fibrous dolomite in the hydrothermal dolostone of the Dengying Formation, central Sichuan Basin, and its response to supercontinent breakup, Minerals, 13, 1353, https://doi.org/10.3390/min13101353, 2023.
Zhong, S. and Mucci, A.: Partitioning of rare earth elements (REEs) between calcite and seawater solutions at 25 °C and 1 atm, and high dissolved REE concentrations, Geochim. Cosmochim. Ac., 59, 443–453, https://doi.org/10.1016/0016-7037(94)00381-U, 1995.
Short summary
This study shows that calcite can trap elements similar to radioactive substances very effectively under natural conditions. By studying a sample formed under nuclear-waste-repository-like conditions, it was found that certain crystal parts hold over 200 times more of these elements. This happens through multiple processes, helping to safely store harmful substances even in low-salt environments, which is important for nuclear waste safety.
This study shows that calcite can trap elements similar to radioactive substances very...