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Gadolinite-(Nd), a New Member of the Gadolinite Supergroup from Fe-REE Deposits of Bastnäs-Type, Sweden

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Gadolinite-(Nd), a New Member of the Gadolinite Supergroup from Fe-REE Deposits of Bastnäs-Type, Sweden Mineralogical Magazine, May 2018, Vol. 82(S1), pp. S133–S145 Gadolinite-(Nd), a new member of the gadolinite supergroup from Fe-REE deposits of Bastnäs-type, Sweden 1,* 2 1 1 3,4 RADEK ŠKODA ,JAKUB PLÁŠIL ,RENATA ČOPJAKOVÁ ,MILAN NOVÁK ,ERIK JONSSON ,MICHAELA 1,5,6 7 VAŠINOVÁ GALIOVÁ AND DAN HOLTSTAM 1 Department of Geological Sciences, Faculty of Science, Masaryk University, Kotlárská̌ 2, CZ-611 37 Brno, Czech Republic 2 Institute of Physics ASCR, v.v.i., Na Slovance 2, Praha 8, CZ-182 21, Czech Republic 3 Department of Mineral Resources, Geological Survey of Sweden, Box 670, SE-751 28 Uppsala, Sweden 4 Department of Earth Sciences, Uppsala University, SE-752 36 Uppsala, Sweden 5 Department of Chemistry, Faculty of Science, Masaryk University, Kotlárská̌ 2, CZ-611 37 Brno, Czech Republic 6 Central European Institute of Technology (CEITEC), Masaryk University, Kamenice 5, CZ-625 00 Brno, Czech Republic 7 Swedish Research Council, Box 1035, SE-101 38 Stockholm, Sweden [Received 26 January 2017; Accepted 7 June 2017; Associate Editor: John Bowles] ABSTRACT A new member of the gadolinite supergroup, gadolinite-(Nd), IMA2016-013, ideally Nd2FeBe2Si2O10,was found in the Malmkärra mine, ∼3.5 km WSW of Norberg, south-central Sweden, where it occurs in association with fluorbritholite-(Ce), västmanlandite-(Ce), dollaseite-(Ce), bastnäsite-(Ce) and tremolite. Gadolinite-(Nd) forms anhedral grains up to 150 µm in size, commonly occurring as aggregates of olive green colour. The crystals are transparent with vitreous to adamantine lustre. Gadolinite-(Nd) is brittle with conchoidal fracture, no cleavage or parting was observed. It has a white streak, the Mohs hardness is 6.5–7 and the calculated density is 4.86 g cm–3. Optically, the mineral is weakly pleochroic in shades of olive – green, biaxial ( ), nα = 1.78(1), nβ(calc.) = 1.80, nγ = 1.81(1) measured in white light, 2V(meas.) = 62(3)°. Electron-microprobe and laser ablation inductively coupled plasma mass spectrometry analysis [in wt.%] provided SiO2 21.77, Y2O3 5.49, La2O3 2.78, Ce2 O3 14.04, Pr2O3 3.28, Nd2O3 19.27, Sm2O3 5.30, Eu2O3 0.24, Gd2O3 4.10, Tb2O3 0.36, Dy2O3 1.32, Ho2O3 0.18, Er2O3 0.38, MgO 0.51, CaO 0.14, MnO 0.10, FeO 10.62, B2O3 0.10, BeOcalc. 8.99, H2Ocalc. 0.55 and total 99.52 giving the following empirical formula (based on 2 Si): (Nd0.632 Ce0.472Y0.268Sm0.168Gd0.125Pr0.110La0.094Dy0.039Ca0.014Er0.011Tb0.011Eu0.008 Ho0.008)∑1.957(Fe0.816Mg0.070Mn0.008)∑0.894(Be1.984B0.016)∑2.000Si2O9.660OH0.337. A weak Raman vibra- tion band at ∼3525 cm–1 confirms the presence of water in the structure. Gadolinite-(Nd) is monoclinic, P2 /c,witha =4.8216(3)Å,b = 7.6985(4) Å, c = 10.1362(6) Å, β = 90.234(4)°, V=376.24(6) Å3 and Z =2. 1 The strongest X-ray diffraction lines are [dobs in Å (hkl) Irel]: 4.830 (100) 72, 3.603 (021) 37, 3.191(112) 52, 3.097 (013) 35, 2.888 (121) 100, 2.607(113) 49, 2.412 (200) 24. Along with the Malmkärra mine, gadolinite- (Nd) was also recorded also at Johannagruvan and Nya Bastnäs. The minerals of the gadolinite subgroup together with fluorbritholite-(Ce) incorporate the highest fraction of medium-to-heavy rare-earth elements among associated rare-earth element minerals in the Malmkärra mine and possibly in all Bastnäs-type deposits. K EYWORDS: gadolinite-(Nd), rare-earth elements, *E-mail:[email protected] new mineral, crystal structure, Malmkärra, Bastnäs- https://doi.org/10.1180/minmag.2017.081.047 type deposits. This paper is part of a special issue entitled ‘Critical-metal mineralogy and ore genesis’. The Geological Survey of Sweden (SGU) has contributed to the costs of Open Access publication for this paper. © The Mineralogical Society 2018. 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. RADEK ŠKODA ET AL. Introduction TABLE 1. Minerals of the gadolinite supergroup and their structural formulae (Bačík et al., 2017). THE mineral gadolinite has a special place in the history of science, and specifically so in chemistry and mineralogy. It was the study of what was then Gadolinite group called “ytterbite” from the Ytterby pegmatite north Datolite subgroup Datolite Ca □B Si O (OH) of Stockholm, Sweden, by the Finnish-Swedish 2 2 2 8 2 Homilite Ca Fe2+B Si O chemist Johan Gadolin (1760–1852), that led to the 2 2 2 10 Gadolinite subgroup first discovery of a rare-earth element (REE) in the 2+ Gadolinite-(Ce) Ce2Fe Be2Si2O10 form of “yttria” (Gadolin, 1794). Gadolin’s yttria 2+ Gadolinite-(Nd) Nd2Fe Be2Si2O10 was later proven to be a mixture of REEs, 2+ Gadolinite-(Y) Y2Fe Be2Si2O10 dominated by yttrium, while the “ytterbite” was □ Hingganite-(Ce) Ce2 Be2Si2O8(OH)2 finally named gadolinite (Ekeberg, 1802), now □ Hingganite-(Y) Y2 Be2Si2O8(OH)2 gadolinite-(Y). Presently, the REEs are very high on □ Hingganite-(Yb) Yb2 Be2Si2O8(OH)2 the European Union’s lists of critical metals (http:// Minasgeraisite-(Y) Y2CaBe2Si2O10 europa.eu/rapid/press-release_IP-14-599_en.htm) Herderite group and neodymium is the most in demand. Systematic Drugmanite subgroup 3+□ research towards the understanding of REE ore- Drugmanite Pb2Fe P2[O7(OH)](OH)2 forming processes, a better knowledge of the Herderite subgroup □ distribution of these metals among the individual Bergslagite Ca2 Be2As2O8(OH)2 □ ore minerals, and the origin of these metals is of Herderite Ca2 Be2P2O8F2 □ increasing interest. Hydroxylherderite Ca2 Be2P2O8(OH)2 The newly-defined gadolinite supergroup (Bačík et al., 2017) includes silicates, phosphates and j arsenates with the general formula A2MQT2O8 2, Alpine-type hydrothermal mineralizations (e.g. where the individual structural sites are occupied as Demartin et al., 1993; Bonazzi et al., 2003;Pršek follows A: Ca, REE (Y + lanthanoids) > U, Th, Pb, et al., 2010), and some iron-oxide skarn deposits Mn2+ and Bi; M:Fe2+, □ (vacancy) > Mg, Mn2+, (e.g. Geijer, 1961; Holtstam and Andersson, 2007). Zn, Cu, Al; Q: Be, B > Li; T: Si > P,As, B, Be, S; j: The members of the gadolinite subgroup with a O, OH > F (Bačík et al., 2017). Based on the T-site magmatic origin are commonly metamict due to occupancy, the gadolinite supergroup is divided significant amounts of actinides substituting for into the gadolinite [Si4+ >(P5+ +As5+)] and herder- REE, which complicates their structural investiga- ite [(P5+ +As5+)>Si4+] groups. Moreover, there are tion. Well-crystalline samples are scarce and two subgroups within the gadolinite group, of usually of a hydrothermal origin (Demartin et al., which the gadolinite subgroup is dominated by 1993). REE3+ cations, and the datolite subgroup is A neodymium-dominant analogue of gadolinite- dominated by divalent cations, in the A site. (Y) or gadolinite-(Ce) was suggested by Holtstam Accordingly, the Q-site is occupied predominantly and Andersson (2007) from Bastnäs-type skarn by Be2+ in the gadolinite subgroup and by B3+ in deposits (Bergslagen ore province, south-central the datolite subgroup. The herderite group is also Sweden), but due to the lackof a sufficient amount of subdivided into the herderite and drugmanite material, they did not provide any data apart from the subgroups (cf. Table 1). chemical microanalyses. This paper provides a full Gadolinite-subgroup minerals (particularly characterization, including chemical composition, gadolinite and hingganite) typically occur in structural, physical and optical properties of the new rather metaluminous, fractionated granitic pegma- mineral gadolinite-(Nd), which was approved tites with a NYF (Niobium-Yttrium-Fluorine; in recently by the Commission on New Minerals, the sense of Černý, 1991) signature (e.g. Bjørlykke, Nomenclature and Classification (CNMNC) of the 1935; Brotzen, 1959; Haynes, 1965; Vorma et al., International Mineralogical Association (IMA), 1966; Nilssen, 1973; Bergstøl and Juve, 1988; under the number 2016-013. The name is given in Smeds, 1990; Kjellman et al., 1999; Pezzotta et al., analogy with the other members of the gadolinite 1999; Miyawaki et al., 2007; Škoda et al., 2012, subgroup (Bačík et al., 2017), as the neodymium- 2015; Pieczka et al., 2015), alkaline rocks (e.g. dominant species. Type material is deposited under Segalstad and Larsen, 1978; Cámara et al., 2008; catalogue number B 11298 at the Moravian Pekov et al., 2007; Lyalina et al., 2014), REE-rich Museum, Brno, Czech Republic. S134 GADOLINITE-(Nd) FROM MALMKÄRRA, SWEDEN Geological setting and the type locality ‘Bastnäs-type deposits’ was introduced by Geijer (1961) to characterize a group of similar, Fe + REE Gadolinite-(Nd) was found in samples from the ± Cu ± Mo ± Bi ± Au mineralized skarns that sup- Malmkärra, Johanna and Nya Bastnäs mines, all posedly have a common origin to the Nya Bastnäs belonging to the Fe-REE ‘Bastnäs-type’ skarn deposit. Based mainly on differences in mineral deposits in the Bergslagen ore province (Geijer, assemblages, Holtstam and Andersson (2007) 1961; Holtstam and Andersson, 2007; Jonsson divided them into two subtypes: deposits of et al., 2014; Holtstam et al., 2014). The present subtype 1 are essentially only enriched in light- mineral characterization was only undertaken on rare-earth elements (LREE), whereas those of material from the Malmkärra mine (60°4′N, 15°51′ subtype 2 are enriched in both light and heavy- E), ∼3.5 km WSWof Norberg due to the very small rare-earth elements (LREE and HREE, respectively). size of gadolinite-(Nd) crystals (<30 µm) at the The Malmkärra deposit (subtype 2) is hosted by other localities. a partly dolomitic marble that forms a conformable The Bastnäs-type deposits occur in the north- interlayer within the surrounding, typically exten- western part of the Bergslagen ore province, south sively altered metavolcanic rocks.
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