Skip to main content Accessibility help

We use cookies to distinguish you from other users and to provide you with a better experience on our websites. Close this message to accept cookies or find out how to manage your cookie settings.

Close cookie message
×
Home
  • Home
Article

Structural state of rare earth elements in eudialyte-group minerals

  • Anouk M. Borst (a1), Adrian A. Finch (a1), Henrik Friis (a2), Nicola J. Horsburgh (a1), Platon N. Gamaletsos (a3) (a4), Joerg Goettlicher (a5), Ralph Steininger (a5) and Kalotina Geraki (a6)...

Abstract

Eudialyte-group minerals (EGM) attract global interest as potential resources for high-field-strength elements (e.g. Zr, Nb, Ta, and rare-earth elements), i.e. critical materials for modern technologies. They are particularly valued for their relative enrichment in the most critical lanthanides, i.e. Nd and heavy rare earth elements (Gd–Lu). However, rare earth element (REE) substitution mechanisms into the EGM structure are still poorly understood. Light and heavy REE may occupy different sites and there may be ordering and/or defect clustering in the structure. This study uses X-ray absorption spectroscopy to determine the structural state of REE in EGM from prospective eudialyte-bearing complexes. Yttrium K-edge and Nd L3-edge spectra were collected as proxies for heavy and light REE, respectively, and compared to natural and synthetic REE-bearing standards. Extended X-ray absorption fine structure data yield best fits for Y in six-fold coordination with Y–O distances of 2.24–2.32 Å, and a second coordination sphere comprising Fe, Na, Ca, Si and O at radial distances of 3.6–3.8 Å. These findings are consistent with dominant Y3+ substitution for Ca2+ on the octahedral M1 site in all the samples studied, and exclude preferential substitution of Y3+ onto the smaller octahedral Z site or the large low-symmetry N4 site.

Using lattice strain theory, we constructed relative partitioning models to predict site preferences of lanthanides we have not measured directly. The models predict that all REE are favoured on the Ca-dominant M1 site and that preferential partitioning of heavy over light REE increases in EGM containing significant Mn in the M1-octahedral rings (oneillite subgroup). Thus, the flat REE profiles that make EGM such attractive exploration targets are not due to preferential partitioning of light and heavy REE onto different sites. Instead, local ordering of Mn- and Ca-occupied M1 sites may influence the capacity of EGM to accommodate heavy REE.

Copyright

COPYRIGHT: © Mineralogical Society of Great Britain and Ireland 2019

Corresponding author

*Author for correspondence: Anouk M. Borst, Email: anoukborst@gmail.com

Footnotes

Hide All

This paper is part of a thematic set arising from the 3rd International Critical Metals Conference (Edinburgh, May 2019).

Associate Editor: Katharina Pfaff

Footnotes

References

Hide All
Adamas Intelligence (2019) Rare Earth Elements: Market Issues and Outlook. Castilloux, R., editor, Adamas Intelligence Report Q2, pp. 1–9.
Balomenos, E., Davris, P., Deady, E., Yang, J., Panias, D., Friedrich, B., Binnemans, K., Seisenbaeva, G., Dittrich, C., Kalvig, P. and Paspaliaris, I. (2017) The EURARE Project: development of a sustainable exploitation scheme for Europe's rare earth ore deposits. Johnson Matthey Technology Review, 61, 142–153.
Binnemans, K., Jones, P.T., Müller, T. and Yurramendi, L. (2018) Rare earths and the balance problem: how to deal with changing markets? Journal of Sustainable Metallurgy, 4, 126–146.
Blundy, J. and Wood, B. (1994) Prediction of crystal-melt partition coefficients from elastic moduli. Nature, 372, 452.
Blundy, J. and Wood, B. (2003) Partitioning of trace elements between crystals and melts. Earth and Planetary Science Letters, 210, 383–397.
Boatner, L.A. (2002) Synthesis, structure, and properties of monazite, pretulite, and xenotime. Pp. 87–121 in: Phosphates (Kohn, M.L., Rakovan, J. and Hughes, J.M., editors). Reviews in Mineralogy & Geochemistry, 48. Mineralogical Society of America and the Geochemical Society, Chantilly, Virginia, USA.
Borst, A.M., Friis, H., Andersen, T., Nielsen, T.F.D., Waight, T.E. and Smit, M.A. (2016) Zirconosilicates in the kakortokites of the Ilímaussaq complex, South Greenland: Implications for fluid evolution and high-field-strength and rare-earth element mineralization in agpaitic systems. Mineralogical Magazine, 80, 5–30.
Borst, A.M., Friis, H., Nielsen, T.F.D. and Waight, T.E. (2018) Bulk and mush melt evolution in agpaitic intrusions: insights from compositional zoning in eudialyte, Ilímaussaq Complex, South Greenland. Journal of Petrology, 59, 589–612.
Brice, J.C. (1975) Some thermodynamic aspects of the growth of strained crystals. Journal of Crystal Growth, 28, 249–253.
Chakhmouradian, A.R. and Wall, F. (2012) Rare earth elements: minerals, mines, magnets (and more). Elements, 8, 333–340.
Davris, P., Stopic, S., Balomenos, E., Panias, D., Paspaliaris, I. and Friedrich, B. (2017) Leaching of rare earth elements from eudialyte concentrate by suppressing silica gel formation. Minerals Engineering, 108, 115–122.
de Groot, F.M.F. (1995) Differences between L3 and L2 X-ray absorption spectra. Physica B: Condensed Matter, 208–209, 15–18.
Díaz-Moreno, S., Muñoz-Páez, A. and Chaboy, J. (2000) X-ray Absorption Spectroscopy (XAS) study of the hydration structure of yttrium(III) cations in liquid and glassy states: Eight or nine-fold coordination? Journal of Physical Chemistry A, 104, 1278–1286.
Downs, R.T. and Hall-Wallace, M. (2003) The American Mineralogist crystal structure database. American Mineralogist, 88, 247–250.
Dura, O.J., Boada, R., López de la Torre, M.A., Aquilanti, G., Rivera-Calzada, A., Leon, C. and Chaboy, J. (2013) XANES and EXAFS study of the local order in nanocrystalline yttria-stabilized zirconia. Physical Review B, 87, 174109.
Estrade, G., Salvi, S., Béziat, D., Rakotovao, S. and Rakotondrazafy, R. (2014) REE and HFSE mineralization in peralkaline granites of the Ambohimirahavavy alkaline complex, Ampasindava peninsula, Madagascar. Journal of African Earth Sciences, 94, 141–155.
Estrade, G., Salvi, S. and Béziat, D. (2018) Crystallization and destabilization of eudialyte-group minerals in peralkaline granite and pegmatite: a case study from the Ambohimirahavavy complex, Madagascar. Mineralogical Magazine, 82, 375–399.
European Commission (2017) Study on the Review of the List of Critical Raw Materials – Final Report. European Union, Luxembourg.
Finch, A.A. and Allison, N. (2007) Coordination of Sr and Mg in calcite and aragonite. Mineralogical Magazine, 71, 539–552.
Finck, N., Bouby, M., Dardenne, K. and Yokosawa, T. (2017) Yttrium co-precipitation with smectite: A polarized XAS and AsFlFFF study. Applied Clay Science, 137, 11–21.
Friis, H. (2009) Luminescence Spectroscopy of Natural and Synthetic REE-Bearing Minerals. PhD Thesis, University of St Andrews, St Andrews, UK.
Friis, H., Finch, A.A., Williams, C.T. and Hanchar, J.M. (2010) Photoluminescence of zircon (ZrSiO 4) doped with REE 3+(REE = Pr, Sm, Eu, Gd, Dy, Ho, Er). Physics and Chemistry of Minerals, 37, 333–342.
Fryer, B. and Edgar, A. (1977) Significance of rare earth distributions in coexisting minerals of peralkaline undersaturated rocks. Contributions to Mineralogy and Petrology, 61, 35–48.
Goodenough, K., Schilling, J., Jonsson, E., Kalvig, P., Charles, N., Tuduri, J., Deady, E., Sadeghi, M., Schiellerup, H. and Müller, A. (2016) Europe's rare earth element resource potential: An overview of REE metallogenetic provinces and their geodynamic setting. Ore Geology Reviews, 72, 838–856.
Goodenough, K.M., Wall, F. and Merriman, D. (2017) The rare earth elements: demand, global resources, and challenges for resourcing future generations. Natural Resources Research, 1–16.
Grice, J.D. and Gault, R.A. (2006) Johnsenite-(CE): A new member of the eudialyte group from Mont Saint-Hilaire, Quebec, Canada. The Canadian Mineralogist, 44, 105–115.
Guiseppetti, G., Mazzi, F. and Tadini, J. (1971) The crystal structure of eudialyte. Tschermaks mineralogische und petrographische Mitteilungen, 16, 105–127.
Hatch, G.P. (2012) Dynamics in the global market for rare earths. Elements, 8, 341–346.
Hazen, RM and Finger, LW (1979) Bulk-modulus-volume relationship for cation-anion polyhedra. Journal of Geophysics Reserach, 84, 6723–6728
Johnsen, O. and Grice, J.D. (1999) The crystal chemistry of the eudialyte group. The Canadian Mineralogist, 37, 865–891.
Johnsen, O., Grice, J.D. and Gault, R.A. (1999) Oneillite; a new Ca-deficient and REE-rich member of the eudialyte group from Mont Saint-Hilaire, Quebec, Canada. The Canadian Mineralogist, 37, 1295–1301.
Johnsen, O., Grice, J.D. and Gault, R.A. (2001) The eudialyte group: a review. Geology of Greenland Survey Bulletin, 190, 65–72.
Johnsen, O., Ferraris, G., Gault, R.A., Grice, J.D., Kampf, A.R. and Pekov, I.V. (2003) The nomenclature of eudialyte-group minerals. The Canadian Mineralogist, 41, 785–794.
Kanno, H. and Hiraishi, J. (1984) Raman study of aqueous rare earth nitrate solutions in liquid and glassy states. The Journal of Physical Chemistry, 88, 2787–2792.
Law, K.M., Blundy, J.D., Wood, B.J. and Ragnarsdottir, K.V. (2000) Trace element partitioning between wollastonite and silicate-carbonate melt. Mineralogical Magazine, 64, 651–661.
Lazdins, K. and Kuzmin, A. (2015) Local structure and lattice dynamics of cubic Y2O3: an x-ray absorption spectroscopy study. IOP Conference Series: Materials Science and Engineering: IOP Publishing, 012031.
Liu, W., Etschmann, B., Migdisov, A., Boukhalfa, H., Testemale, D., Müller, H., Hazemann, J.-L. and Brugger, J. (2017) Revisiting the hydrothermal geochemistry of europium (II/III) in light of new in situ XAS spectroscopy results. Chemical Geology, 459, 61–74.
Machacek, E. and Kalvig, P. (2016) Assessing advanced rare earth element-bearing deposits for industrial demand in the EU. Resources Policy, 49, 186–203.
Mariano, A.N. and Mariano, A. Jr (2012) Rare earth mining and exploration in North America. Elements, 8, 369–376.
Marks, M.A.W. and Markl, G. (2017) A global review on agpaitic rocks. Earth-Science Reviews, 173, 229–258.
Mitchell, R.H. and Liferovich, R.P. (2006) Subsolidus deuteric/hydrothermal alteration of eudialyte in lujavrite from the Pilansberg alkaline complex, South Africa. Lithos, 91, 352–372.
Möller, V. and Williams-Jones, A.E. (2016) Petrogenesis of the Nechalacho Layered Suite, Canada: magmatic evolution of a REE–Nb-rich nepheline syenite intrusion. Journal of Petrology, 57, 229–276.
Möller, V. and Williams-Jones, A.E. (2017) Magmatic and hydrothermal controls on the mineralogy of the basal zone, Nechalacho REE–Nb–Zr deposit, Canada. Economic Geology, 112, 1823–1856.
Mosselmans J.F.W., Quinn, Dent, P.D., A.J., Cavill, S.A., Moreno, S.D., Peach, A., Leicester, P.J., Keylock, S.J., Gregory, S.R., Atkinson, K.D. and Rosell, J.R. (2009) I18 – the microfocus spectroscopy beamline at the Diamond Light Source. Journal of Synchrotron Radiation, 16, 818–824.
Newville, M. (2001) IFEFFIT: interactive XAFS analysis and FEFF fitting. Journal of Synchrotron Radiation, 8, 322–324.
Ni, Y., Hughes, J.M. and Mariano, A.N. (1995) Crystal chemistry of the monazite and xenotime structures. American Mineralogist, 80, 21–26.
Paulick, H. and Machacek, E. (2017) The global rare earth element exploration boom: An analysis of resources outside of China and discussion of development perspectives. Resources Policy, 52, 134–153.
Persson, I., D'Angelo, P., De Panfilis, S., Sandström, M. and Eriksson, L. (2008) Hydration of lanthanoid (III) ions in aqueous solution and crystalline hydrates studied by EXAFS spectroscopy and crystallography: The myth of the “gadolinium break”. Chemistry – A European Journal, 14, 3056–3066.
Pfaff, K., Krumrei, T., Marks, M., Wenzel, T., Rudolf, T. and Markl, G. (2008) Chemical and physical evolution of the ‘lower layered sequence’ from the nepheline syenitic Ilímaussaq intrusion, South Greenland: Implications for the origin of magmatic layering in peralkaline felsic liquids. Lithos, 106, 280–296.
Pfaff, K., Wenzel, T., Schilling, J., Marks, M. and Markl, G. (2010) A fast and easy-to-use approach to cation site assignment for eudialyte group minerals. Neues Jahrbuch fur Mineralogie, 187, 69–81.
Rastsvetaeva, R. (2007) Structural mineralogy of the eudialyte group: A review. Crystallography Reports, 52, 47–64.
Rastsvetaeva, R.K. and Chukanov, N.V. (2012) Classification of eudialyte-group minerals. Geology of Ore Deposits, 54, 487–497.
Rastsvetaeva, R., Aksenov, S. and Chukanov, N. (2010) Crystal structure of the Mn analogue of raslakite, a new representative of the eudialyte group. Doklady Chemistry, 76–81.
Rastsvetaeva, R.K., Aksenov, S.M. and Rozenberg, K.A. (2015) Crystal structure and genesis of the hydrated analog of rastsvetaevite. Crystallography Reports, 60, 831–840.
Rastsvetaeva, R.K., Rozenberg, K.A., Chukanov, N.V. and Aksenov, S.M. (2017) Crystal structure of ilyukhinite, a new mineral of the eudialyte group. Crystallography Reports, 62, 60–65.
Ravel, B. and Newville, M. (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. Journal of Synchrotron Radiation, 12, 537–541.
Roskill, (2018) Rare Earths, Global Industry, Market and Outlooks 2018. London, United Kingdom.
Santos, C., Strecker, K., Suzuki, P., Kycia, S., Silva, O. and Silva, C. (2005) Stabilization of α-SiAlONs using a rare-earth mixed oxide (RE2O3) as sintering additive. Materials Research Bulletin, 40, 1094–1103.
Schilling, J., Wu, F.-Y., McCammon, C., Wenzel, T., Marks, M.A.W., Pfaff, K., Jacob, D.E. and Markl, G. (2011) The compositional variability of eudialyte-group minerals. Mineralogical Magazine, 75, 87–115.
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica A, 32, 751–767.
Sjöqvist, A.S., Cornell, D.H., Andersen, T., Erambert, M., Ek, M. and Leijd, M. (2013) Three compositional varieties of rare-earth element ore: eudialyte-group minerals from the Norra Kärr Alkaline Complex, Southern Sweden. Minerals, 3, 94–120.
Smith, M.P., Moore, K., Kavecsánszki, D., Finch, A.A., Kynicky, J. and Wall, F. (2016) From mantle to critical zone: A review of large and giant sized deposits of the rare earth elements. Geoscience Frontiers, 7, 315–334.
Stark, T., Silin, I. and Wotruba, H. (2016) Mineral processing of eudialyte ore from Norra Kärr. Journal of Sustainable Metallurgy, 3, 32–38.
Stromeyer, F. (1819) Summary of Meeting 16 December 1819. Gottingische gelehrte Anzeigen, 3, 1993–2000.
Tanaka, K., Takahashi, Y. and Shimizu, H. (2008) Local structure of Y and Ho in calcite and its relevance to Y fractionation from Ho in partitioning between calcite and aqueous solution. Chemical Geology, 248, 104–113.
Tanaka, K., Takahashi, Y. and Shimizu, H. (2009) Determination of the host phase of rare earth elements in natural carbonate using X-ray absorption near-edge structure. Geochemical Journal, 43, 143–149.
van de Ven, M.A.J., Borst, A.M., Davies, G.R., Hunt, E.J. and Finch, A.A. (2019) Hydrothermal alteration of eudialyte–hosted critical metal deposits: fluid source and implications for deposit grade. Minerals, 9, 422.
Voßenkaul, D., Birich, A., Müller, N., Stoltz, N. and Friedrich, B. (2017) Hydrometallurgical processing of eudialyte bearing concentrates to recover rare earth elements via low-temperature dry digestion to prevent the silica gel formation. Journal of Sustainable Metallurgy, 3, 79–89.
Wood, B.J. and Blundy, J.D. (1997) A predictive model for rare earth element partitioning between clinopyroxene and anhydrous silicate melt. Contributions to Mineralogy and Petrology, 129, 166–181.
Wood, B.J. and Blundy, J.D. (2001) The effect of cation charge on crystal–melt partitioning of trace elements. Earth and Planetary Science Letters, 188, 59–71.
Wood, B.J. and Blundy, J.D. (2014) Trace element partitioning: the influences of ionic radius, cation charge, pressure, and temperature. Pp. 421–448 in: Treatise on Geochemistry (Second Edition) (Holland, H.D. and Turekian, K.K., editors). Elsevier, Oxford, UK.
Wyckoff, R.W.G. (1964) Crystal Structures. Krieger, New York.

Keywords

Type Description Title
UNKNOWN
Supplementary materials

Borst et al. supplementary material
Borst et al. supplementary material

 Unknown (2.3 MB)
2.3 MB

Structural state of rare earth elements in eudialyte-group minerals

  • Anouk M. Borst (a1), Adrian A. Finch (a1), Henrik Friis (a2), Nicola J. Horsburgh (a1), Platon N. Gamaletsos (a3) (a4), Joerg Goettlicher (a5), Ralph Steininger (a5) and Kalotina Geraki (a6)...

Metrics

Altmetric attention score

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed