Home Physical Sciences Why natural monazite never becomes amorphous: Experimental evidence for alpha self-healing
Article
Licensed
Unlicensed Requires Authentication

Why natural monazite never becomes amorphous: Experimental evidence for alpha self-healing

  • Anne-Magali Seydoux-Guillaume EMAIL logo , Xavier Deschanels , Cédric Baumier , Stefan Neumeier , William John Weber and Sylvain Peuget
Published/Copyright: April 30, 2018
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 103 Issue 5

Abstract

Monazite, a common accessory rare-earth orthophosphate mineral in the continental crust widely used in U-Pb geochronology, holds promise for (U-Th)/He thermochronology and for the immobilization of Pu and minor actinides (MA) coming from spent nuclear fuel reprocessing. Previous results obtained on natural and plutonium-doped monazite have demonstrated the ability of this structure to maintain a crystalline state despite high radiation damage levels. However, the low critical temperature (180 °C), above which amorphization cannot be achieved in natural monazite under ion irradiation, does not explain this old and unsolved paradox: why do natural monazites, independent of their geological history, remain crystalline even when they did not experience any thermal event that could heal the defects? This is what the present study aims to address. Synthetic polycrystals of LaPO4-monazite were irradiated sequentially and simultaneously with α particles (He) and gold (Au) ions. Our results demonstrate experimentally for the first time in monazite, the existence of the defect recovery mechanism, called α-healing, acting in this structure due to electronic energy loss of α particles, which explains the absence of amorphization in natural monazite samples. This mechanism is critically important for monazite geo- and thermochronology and to design and predictively model the long-term behavior of ceramic matrices for nuclear waste conditioning.

Keywords: Monazite, α self-healing; in situ TEM irradiation; dual-ion beam irradiation; helium; geochronology; thermochronology; nuclear waste

Acknowledgments

Experiment performed at the CSNSM facility: JANNuS-Orsay/SCALP platform (CSNSM Univ Paris-Sud/CNRS, Orsay, France). We thank V. Picot-Magnin (ISTerre, CNRS, France) for the synthesis of monazite samples. This experiment was supported by the EMIR French accelerator network. This work was partly supported by the french RENATECH network. Two of the authors were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Materials Science and Engineering Division (W.J.W.) and the German Federal Ministry of Education and Research (BMBF), grant no. 02NUK021A (S.N.), respectively. NEEDS-CNRS is thanked for financial support. E. Gardès is thanked for the long and exciting discussion on diffusion. Two anonymous reviewers are thanked for their constructive comments. The associated editor, Ian Swainson, is also thanked for his helpful editorial handling.

References cited

Boatner, L.A., and Sales B.C. (1988) Monazite. In W. Lutze and R.C. Ewing, Eds., Radioactive Waste Forms for the Future, p. 495–564. Elsevier.Search in Google Scholar

Cherniak, D.J., and Watson, E.B. (2013) Diffusion of helium in natural monazite, and preliminary results on He diffusion in synthetic light rare earth phosphates. American Mineralogist, 98, 1407–1420.10.2138/am.2013.4353Search in Google Scholar

Clavier, N., Podor, R., and Dacheux, N. (2011) Crystal chemistry of the monazite structure. Journal of European Ceramic Society, 31, 941–976.10.1016/j.jeurceramsoc.2010.12.019Search in Google Scholar

Dacheux, N., Clavier, N., and Podor, R. (2013) Monazite as a promising long-term radioactive waste matrix: benefits of high-structural flexibility and chemical durability. American Mineralogist, 98, 833–847.10.2138/am.2013.4307Search in Google Scholar

Deschanels, X., Seydoux-Guillaume, A.M., Magnin, V., Mesbah, A., Tribet, M., Moloney, M., Serruys, Y., and Peuget, S. (2014) Swelling induced by alpha decay in monazite and zirconolite ceramics: a XRD and TEM comparative study. Journal of Nuclear Materials, 448, 184–194.10.1016/j.jnucmat.2014.02.003Search in Google Scholar

Ehlert, T.C., Appaji Gowda, K., Karioris, F.G., and Cartz, L. (1983) Differential scanning calorimetiy of heavy ion bombarded synthetic monazite. Radiation Effects, 70, 173–181.10.1080/00337578308219214Search in Google Scholar

Ewing, R.C., and Wang, L.M. (2002) Phosphates as nuclear waste forms. Reviews in Mineralogy and Geochemistry, 48, 673–699.10.2138/rmg.2002.48.18Search in Google Scholar

Ewing, R.C., Meldrum, A., Wang, L.M., and Wang, S.X. (2000) Radiation induced amorphization. Reviews in Mineralogy and Geochemistry, 39, 319–361.10.1515/9781501509155-013Search in Google Scholar

Farley, K.A. (2007) He diffusion systematics in minerals: Evidence from synthetic monazite and zircon structure phosphates. Geochimica et Cosmochimica Acta, 71, 4015–4024.10.1016/j.gca.2007.05.022Search in Google Scholar

Farley, K.A., and Stockli, D.F. (2002) (U-Th)/He dating of phosphates: apatite, monazite, and xenotime. Reviews in Mineralogy and Geochemistry, 47, 559–577.10.2138/rmg.2002.48.15Search in Google Scholar

Fougerouse, D., Reddy, S.M., Saxey, D.W., Erickson, T.M., Kirkland, C.L., Rickard, W.A., Seydoux-Guillaume, A.M., Clark, C., and Buick, I.S. (2018). Nanoscale distribution of Pb in monazite revealed by atom probe microscopy. Chemical Geology. 10.1016/j.chemgeo.2018.01.020.Search in Google Scholar

Gardés, E., Jaoul, O., Montel, J.-M., Seydoux-Guillaume, A.-M., and Wirth, R. (2006) Pb diffusion in monazite: An experimental study of Pb2+ + Th4+ ⇔ 2Nd3+ interdiffusion. Geochimica et Cosmochimica Acta, 70(9), 2325–2336.10.1016/j.gca.2006.01.018Search in Google Scholar

Gerin, C., Gautheron, C., Oliviero, E., Bachelet, C., Mbongo-Djimbi, D., Seydoux-Guillaume, A.M., Tassan-Got, L., Sarda, P., Roques, J., and Garrido, F. (2017) Influence of vacancy damage on He diffusion in apatite, investigated at atomic to mineralogical scales. Geochimica et Cosmochimica Acta, 197, 87–103.10.1016/j.gca.2016.10.018Search in Google Scholar

Karioris, F.G., Appaji Gowda, K., and Cartz, L. (1981) Heavy ion bombardment of monoclinic ThSiO4, ThO2 and monazite. Radiation Effects Letters, 58, 1–3.10.1080/01422448108226520Search in Google Scholar

Li, W., Shen, Y., Zhou, Y., Nan, S., Chen, C.-H., and Ewing, R.C. (2017) In situ TEM observation of alpha particle induced annealing of radiation damage in Durango apatite. Scientific Report, 7, 14108.10.1038/s41598-017-14379-9Search in Google Scholar

Luo, J.S., and Liu, G.K. (2001) Microscopic effects of self-radiation damage in 244Cm-doped LuPO4 crystals. Journal of Material Research, 16, 366–372.10.1557/JMR.2001.0056Search in Google Scholar

Lumpkin, G.R. (2006) Ceramic waste forms for actinides. Elements, 2, 365–372.10.2113/gselements.2.6.365Search in Google Scholar

Meldrum, A., Boatner, L.A., and Ewing, R.C. (1997a) Displacive radiation effects in the monazite-and zircon-structure orthophosphates. Physical Review B, 13805–13814.10.1103/PhysRevB.56.13805Search in Google Scholar

Meldrum, A., Boatner, L.A., and Ewing, R.C. (1997b) Electron-irradiation-induced nucleation and growth in amorphous LaPO4, ScPO4, and zircon. Journal of Materials Research, 12, 1816–1827.10.1557/JMR.1997.0250Search in Google Scholar

Meldrum, A., Wang, L.M., and Ewing, R.C. (1996) Ion-beam-induced amorphization of monazite. Nuclear Instruments and Methods B, 116, 220–224.10.1016/0168-583X(96)00037-7Search in Google Scholar

Meldrum, A., Zinkle, S.J., Boatner, L.A., and Ewing, R.C. (1999) Heavy-ion irradiation effects in the ABO4 orthosilicates: decomposition, amorphization, and recrystallization. Physical Review B, 59, 3981–3992.10.1103/PhysRevB.59.3981Search in Google Scholar

Mir, A.H., Peuget, S., Toulemonde, M., Bulot, P., Jegou, C., Miro, S., and Bouffard, S. (2015) Defect recovery and damage reduction in borosilicate glasses under double ion beam irradiation. EPL, 112, 36002.10.1209/0295-5075/112/36002Search in Google Scholar

Oelkers, E.H., and Montel, J.-M. (2008) Phosphates and nuclear waste storage. Elements, 4, 113–116.10.2113/GSELEMENTS.4.2.113Search in Google Scholar

Ouchani, S., Dran, J.-C., and Chaumont, J. (1998) Exfoliation and diffusion following helium ion implantation in fluorapatite: implications for radiochronology and radioactive waste disposal. Applied Geochemistry, 13, 707–714.10.1016/S0883-2927(97)00078-4Search in Google Scholar

Parrish, R.R. (1990) U-Pb dating of monazite and its application to geological problems. Canadian Journal of Earth Science, 27, 1431–1450.10.1139/e90-152Search in Google Scholar

Peterman, E.M., Hourigan, J.K., and Grove, M. (2014) Experimental and geologic evaluation of monazite (U–Th)/He thermochronometry: Catnip Sill, Catalina Core Complex, Tucson, AZ. Earth and Planetary Science Letters, 403, 48–55.10.1016/j.epsl.2014.06.020Search in Google Scholar

Picot, V., Deschanels, X., Peuget, S., Glorieux, B., Seydoux-Guillaume, A.M., and Wirth, R. (2008) Ion beam radiation effects in monazite. Journal of Nuclear Materials, 381, 290–296.10.1016/j.jnucmat.2008.09.001Search in Google Scholar

Seydoux-Guillaume, A.M., Wirth, R., Nasdala, L., Gottschalk, M., Montel, J.M., and Heinrich, W. (2002) An XRD, TEM and Raman study of experimentally annealed natural monazite. Physics and Chemistry of Minerals, 29, 240–253.10.1007/s00269-001-0232-4Search in Google Scholar

Seydoux-Guillaume, A.M., Goncalves, P., Wirth, R., and Deutsch, A. (2003) TEM study of polyphasic and discordant monazites: site specific specimen preparation using the Focused Ion Beam technique. Geology, 31, 973–976.10.1130/G19582.1Search in Google Scholar

Seydoux-Guillaume, A.M., Wirth, R., Deutsch, A., and Schärer, U. (2004) On the microstructure of up to 2 Ga old concordant monazites: a X-ray diffraction and transmission electron microscope study. Geochimica et Cosmochimica Acta, 68, 2517–2527.10.1016/j.gca.2003.10.042Search in Google Scholar

Seydoux-Guillaume, A.-M., Bingen, B., Bosse, V., Janots, E., and Laurent, A.T. (2018) Transmission Electron Microscope imaging sharpens geochronological interpretation of zircon and monazite. In D.E. Moser, F. Corfu, J.R. Darling, S.M. Reddy, and K.T. Tait, Eds., Microstructural Geochronology: Planetary Records Down to Atom Scale, 232, p. 261–275. AGU/Wiley Publishing.10.1002/9781119227250.ch12Search in Google Scholar

Soulet, S., Carpena, J., Chaumont, J., Kaitasov, O., Ruault, M.-O., and Krupa, J.C. (2001) Simulation of the alpha-annealing effect in apatitic structures by He-ion irradiation: influence of the silicate/phosphate ratio and of the OH/F substitution. Nuclear Instruments and Methods B, 184, 383–390.10.1016/S0168-583X(01)00764-9Search in Google Scholar

Weber, W.J. (1990) Radiation-induced defects and amorphization in zircon. Journal of Material Research, 5, 2687–2697.10.1557/JMR.1990.2687Search in Google Scholar

Weber, W.J., Ewing, R.C., Catlow, C.R.A., de la Rubia, T.D., Hobbs, L.W., Kinoshita, C., Matzke, H., Motta, A.T., Nastasi, M., Salje, E.K.H., Vance, E.R., and Zinkle, S.J. (1998) Radiation effects in crystalline ceramics for the immobilization of high-level nuclear waste and plutonium. Journal of Material Research, 13, 1434–1484.10.1557/JMR.1998.0205Search in Google Scholar

Weber, W.J., Duffy, D.M., Thomé, L., and Zhang, Y. (2015) The role of electronic energy loss in ion beam modification of materials. Current Opinion in Solid State and Materials Science, 19, 1–11.10.1016/j.cossms.2014.09.003Search in Google Scholar

Weise, C., van den Boogaart, K., Jonckheere, R., and Ratschbacher, L. (2009) Annealing kinetics of Kr-tracks in monazite: Implications for fission-track modelling. Chemical Geology, 260, 129–137.10.1016/j.chemgeo.2008.12.014Search in Google Scholar

Zhang, Y., Sachan, R., Pakarinen, O.H., Chisholm, M.F., Liu, P., Xue, H., and Weber, W.J. (2015) Ionization-induced annealing of pre-existing defects in silicon carbide. Nature Communications, 6, 8049.10.1038/ncomms9049Search in Google Scholar PubMed PubMed Central

Received: 2017-12-22
Accepted: 2018-2-14
Published Online: 2018-4-30
Published in Print: 2018-5-25

© 2018 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Review
  2. Biosilica as a source for inspiration in biological materials science
  4. Ab initio study of water speciation in forsterite: Importance of the entropic effect
  6. Surface-modified phillipsite-rich tuff from the Campania region (southern Italy) as a promising drug carrier: An ibuprofen sodium salt trial
  8. Structure of low-order hemimorphite produced in a Zn-rich environment by cyanobacterium Leptolingbya frigida
  10. Formation of dolomite catalyzed by sulfate-driven anaerobic oxidation of methane: Mineralogical and geochemical evidence from the northern South China Sea
  12. Anisotropic growth of olivine during crystallization in basalts from Hawaii: Implications for olivine fabric development
  14. Melting experiments on Fe–Si–S alloys to core pressures: Silicon in the core?
  16. High-pressure phase behavior and equations of state of ThO2 polymorphs
  18. Mafic inputs into the rhyolitic magmatic system of the 2.08 Ma Huckleberry Ridge eruption, Yellowstone
  20. Toward the wider application of 29Si NMR spectroscopy to paramagnetic transition metal silicate minerals and glasses: Fe(II), Co(II), and Ni(II) silicates
  22. Equations of state and phase boundary for stishovite and CaCl2-type SiO2
  24. Insight on gem opal formation in volcanic ash deposits from a supereruption: A case study through oxygen and hydrogen isotopic composition of opals from Lake Tecopa, California, U.S.A
  26. Revisiting the crystal structure of dickite: X-ray diffraction, solid-state NMR, and DFT calculations study
  28. Temperature and pressure effects on the partitioning of V and Sc between clinopyroxene and silicate melt: Implications for mantle oxygen fugacity
  29. Letter
  30. Why natural monazite never becomes amorphous: Experimental evidence for alpha self-healing
  32. New Mineral Names
  33. Book Review
  34. Book Review: Glaciovolcanism on Earth and Mars: Products, Processes and Paleoenvironmental Significance
https://doi.org/10.2138/am-2018-6447
Keywords for this article
Monazite, α self-healing; in situ TEM irradiation; dual-ion beam irradiation; helium; geochronology; thermochronology; nuclear waste

Articles in the same Issue

  1. Review
  2. Biosilica as a source for inspiration in biological materials science
  4. Ab initio study of water speciation in forsterite: Importance of the entropic effect
  6. Surface-modified phillipsite-rich tuff from the Campania region (southern Italy) as a promising drug carrier: An ibuprofen sodium salt trial
  8. Structure of low-order hemimorphite produced in a Zn-rich environment by cyanobacterium Leptolingbya frigida
  10. Formation of dolomite catalyzed by sulfate-driven anaerobic oxidation of methane: Mineralogical and geochemical evidence from the northern South China Sea
  12. Anisotropic growth of olivine during crystallization in basalts from Hawaii: Implications for olivine fabric development
  14. Melting experiments on Fe–Si–S alloys to core pressures: Silicon in the core?
  16. High-pressure phase behavior and equations of state of ThO2 polymorphs
  18. Mafic inputs into the rhyolitic magmatic system of the 2.08 Ma Huckleberry Ridge eruption, Yellowstone
  20. Toward the wider application of 29Si NMR spectroscopy to paramagnetic transition metal silicate minerals and glasses: Fe(II), Co(II), and Ni(II) silicates
  22. Equations of state and phase boundary for stishovite and CaCl2-type SiO2
  24. Insight on gem opal formation in volcanic ash deposits from a supereruption: A case study through oxygen and hydrogen isotopic composition of opals from Lake Tecopa, California, U.S.A
  26. Revisiting the crystal structure of dickite: X-ray diffraction, solid-state NMR, and DFT calculations study
  28. Temperature and pressure effects on the partitioning of V and Sc between clinopyroxene and silicate melt: Implications for mantle oxygen fugacity
  29. Letter
  30. Why natural monazite never becomes amorphous: Experimental evidence for alpha self-healing
  32. New Mineral Names
  33. Book Review
  34. Book Review: Glaciovolcanism on Earth and Mars: Products, Processes and Paleoenvironmental Significance
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2026 De Gruyter Brill
Downloaded on 28.2.2026 from https://www.degruyterbrill.com/document/doi/10.2138/am-2018-6447/html
Scroll to top button