Mineralogical Magazine (2020), 84,19–34 doi:10.1180/mgm.2019.50 Article Structural state of rare earth elements in eudialyte-group minerals Anouk M. Borst1* , Adrian A. Finch1 , Henrik Friis2 , Nicola J. Horsburgh1, Platon N. Gamaletsos3,4 , Joerg Goettlicher5, Ralph Steininger5 and Kalotina Geraki6 1School of Earth and Environmental Sciences, University of St Andrews, North Street, St Andrews KY16 9AL, United Kingdom; 2Natural History Museum, University of Oslo, Oslo, Postboks 1172, Blindern 0318 Oslo, Norway; 3Department of Materials Engineering, KU Leuven, Kasteelpark Arenberg 44, 3001 Leuven, Belgium; 4Center for Electron Nanoscopy, Technical University of Denmark, 2800 Kongens Lyngby, Denmark; 5Institute for Photon Science and Synchrotron Radiation, Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen, Germany; and 6Science Division, Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0DE, United Kingdom 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. Keywords: critical metals, eudialyte-group minerals, peralkaline igneous rocks, rare earth elements, partitioning models, lattice strain theory, XANES, EXAFS, X-ray absorption spectroscopy, high-field-strength elements (Received 7 April 2019; accepted 26 July 2019; Accepted Manuscript published online: 2 August 2019; Associate Editor: Katharina Pfaff) Introduction Eudialyte-group minerals, their alteration products and asso- ciated mineral assemblages are of significant economic interest Eudialyte-group minerals (EGM) are Na-Ca-Zr-cyclosilicates that as they provide potential low-cost resources for elements such accommodate many elements in their complex trigonal crystal as Zr, REE, Nb and Ta. These metals have a wide variety of structure. In addition to the essential constituents Na, Ca, Zr uses in modern technologies, ranging from durable alloys, per- and Si, they host significant amounts of Fe, Mn, REE, Y, Nb, manent magnets, catalysts and energy-efficient lighting phos- Hf, Ti, K, Sr and Ti as well as Cl, F, H O and OH groups 2 phors to rechargeable batteries, and thus crucial enablers of the (Johnsen and Grice, 1999). Consequently, the eudialyte group clean energy and transport transition. Rare earth elements, in encompasses a wide range of minerals of varying compositions particular, are considered critical metals due to challenges in and space groups (Rastsvetaeva and Chukanov, 2012), which at their supply chain and a projected growth in demand present includes over 28 species accepted by the International (Chakhmouradian and Wall, 2012; Hatch, 2012; European Mineralogical Association (IMA), reported from c. 105 localities Commission, 2017; Goodenough et al., 2017; Roskill, 2018; worldwide (Marks and Markl, 2017). Adamas Intelligence, 2019). Significant deposits of EGM are found in peralkaline igneous complexes such as: Ilímaussaq (Greenland); Norra Kärr (Sweden); Lovozero and Khibina *Author for correspondence: Anouk M. Borst, Email: [email protected] (Russia); Kipawa (Canada); and Pajarito (USA) (e.g. Mariano and This paper is part of a thematic set arising from the 3rd International Critical Metals Mariano Jr, 2012; Sjöqvist et al., 2013; Machacek and Kalvig, Conference (Edinburgh, May 2019). 2016; Goodenough et al., 2016; Smith et al., 2016; Marks and Cite this article: Borst A.M., Finch A.A., Friis H., Horsburgh N.J., Gamaletsos P.N., Markl, 2017; Borst et al., 2018). Eudialyte represents a relatively Goettlicher J., Steininger R. and Geraki K. (2020) Structural state of rare earth elements ∼ – ∼ in eudialyte-group minerals. Mineralogical Magazine 84,19–34. https://doi.org/10.1180/ low-grade ore mineral ( 1 10 wt.% total REE2O3, 1 wt.% of mgm.2019.50 Nb2O5 and <0.5 wt.% Ta2O5) compared to carbonatite-hosted © The Author(s) 2019. This is an Open Access article, distributed under the terms of the Creative Commons Attribution licence (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted re-use, distribution, and reproduction in any medium, provided the original work is properly cited. 20 Anouk M. Borst et al. REE ore minerals, but their economic importance is enhanced by predominantly occupy 4- or 5-coordinated M2 sites, respectively, relatively high proportions of the more valuable (i.e. more critical) in planar squares or five vertex-pyramids between the six- heavy rare earth elements (HREE) relative to the light rare earth membered rings (Guiseppetti et al., 1971; Johnsen and Grice, elements (LREE) (Fryer and Edgar, 1977; Binnemans et al., 2018), 1999; Rastsvetaeva and Chukanov, 2012; Rastsvetaeva, 2007). as well as relatively low U and Th contents (Schilling et al., 2011) Ordering of elements on the various sites gives rise to a wide and ease of extraction through magnetic separation (Goodenough range of EGM compositions and structural hettotypes, predomin- et al., 2017; Paulick and Machacek, 2017). Recent efforts to improve antly within the R3m, R3m and R3 space groups (Rastsvetaeva, the metallurgical processing of eudialyte focused on resolving 2007, Rastsvetaeva and Chukanov, 2012). issues with the formation of silica gels which hinders metal extraction. The IMA-accepted formula for the eudialyte group is: Θ + Innovative multi-step leaching techniques have been developed and N15–16[M1]6[M2]3[M3][M4]Z3Si24O66–73( )0–9(X)2,where:N =Na , + 2+ 2+ 3+ □ 2+ 2+ + promise potential for upscaling, though economic viability has yet K ,Sr ,Ca , REE , (vacancy), Ba ,Mn or H3O ; to be demonstrated at industry scales (Stark et al., 2016; Balomenos M1=Ca2+, REE3+,Mn2+,Fe2+,Na+,Sr2+; M2=Fe2+,Mn2+, + □ + 4+ 5+ 4+ + 2+ 3+ 4+ et al., 2017;Davriset al., 2017; Voßenkaul et al., 2017). Na , ,H3O ,Zr ,Ta ,Ti ,K,Ba or Fe ; M3/4 = Si , At the heart of eudialyte’s commercial value is its relatively flat Al3+,Nb5+,Ti4+,W6+ or Na+, Z =Zr4+,Hf4+,Ti4+ or Nb5+; Θ – 2– 2– 2– 4– – – chondrite-normalised REE profile (Chakhmouradian and Wall, =H2O, OH ,O ,CO3 ,SO4 or SiO4 ; and X =Cl ,F or – 2012, Fryer and Edgar, 1977). Partitioning of REE in minerals typ- OH (Johnsen et al., 2003). ically produces parabolic or curved profiles (due to partitioning Empirical formulae are calculated on the basis of 29 cations for behaviour as a function of ionic radius, e.g. Blundy and Wood, the sum of Si, Al, Zr, Ti, Hf, Nb, W and Ta. At present, 200 years 2003) and the unusually flat to HREE-enriched profiles in EGM after eudialyte was first reported (Stromeyer, 1819), the eudialyte hints at substitutions into multiple sites, site ordering and/or group comprises 28 independent IMA-approved mineral species, defect clustering. Furthermore, the open literature is inconsistent and new ones are described regularly (e.g. Rastsvetaeva et al., as to whether REE substitute on the Na, Ca or Zr sites, or a com- 2015, 2017). It is worth noting that the number of crystallo- bination of these (Johnsen and Grice, 1999; Johnsen et al., 2001; graphically non-equivalent sites increases in non-centrosymmetric Rastsvetaeva, 2007; Pfaff et al., 2008; Möller and Williams-Jones, space groups. Common species of EGM include eudialyte sensu 2016). Such considerations are more than academic – EGM stricto, kentbrooksite, ferrokentbrooksite, alluaivite, oneillite and deposits are commonly altered (Mitchell and Liferovich, 2006; (Mn-) raslakite (Table 1), with natural samples showing solid Borst et al., 2016; Möller and Williams-Jones, 2017; Estrade solution between end-members. et al., 2018; van de Ven et al., 2019) and some replacement pro- Of the many trace elements that substitute into eudialyte-group cesses are topotactic (i.e. retaining structural templates from the minerals, the REE are particularly significant, and can reach up to primary structure to the secondary). Furthermore, the silica-gels 10 wt.% REE2O3 (Grice and Gault, 2006). However, their exact that form during eudialyte dissolution (e.g. Voßenkaul et al., location has been unclear. In eudialyte s.s.theREE are inferred 2017; Davris et al., 2017) may preserve structural states from to substitute for Ca on the M1 site, while in kentbrooksite, oneillite the original eudialyte. There is therefore a commercial imperative and raslakite, the REE are inferred to occupy both the N and M1 that REE substitution in eudialyte is fully understood.