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Article Benefited from Construc- Ering the Co Dominance Among the Non-Cu Metal Atoms, Tive Reviews by Jochen Schlüter and Taras Panikorovskii

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Article Benefited from Construc- Ering the Co Dominance Among the Non-Cu Metal Atoms, Tive Reviews by Jochen Schlüter and Taras Panikorovskii Eur. J. Mineral., 32, 637–644, 2020 https://doi.org/10.5194/ejm-32-637-2020 © Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License. Gobelinite, the Co analogue of ktenasite from Cap Garonne, France, and Eisenzecher Zug, Germany Stuart J. Mills1, Uwe Kolitsch2,3, Georges Favreau4, William D. Birch1, Valérie Galea-Clolus5, and Johannes Markus Henrich6 1Geosciences, Museums Victoria, GPO Box 666, Melbourne, Victoria 3001, Australia 2Mineralogisch-Petrographische Abt., Naturhistorisches Museum, Burgring 7, 1010 Vienna, Austria 3Institut für Mineralogie und Kristallographie, Universität Wien, Althanstraße 14, 1090 Vienna, Austria 4independent researcher: 421 Avenue Jean Monnet, 13090 Aix-en-Provence, France 5independent researcher: 10 rue Combe Noire, 83210 Solliès-Toucas, France 6independent researcher: Im Großen Garten 3, 57548 Kirchen (Sieg), Germany Correspondence: Stuart J. Mills ([email protected]) Received: 13 April 2020 – Revised: 30 October 2020 – Accepted: 9 November 2020 – Published: 25 November 2020 Abstract. The new mineral gobelinite, ideally CoCu4.SO4/2.OH/6 6H2O, is a new member of the ktenasite group and the Co analogue of ktenasite, ZnCu4.SO4/2.OH/6 6H2O.q It occurs at Cap Garonne (CG), Var, France (type locality), and Eisenzecher Zug (EZ), Siegerland, Northq Rhine-Westphalia, Germany (cotype lo- cality). The mineral forms pale green, bluish green or greyish green, blocky to thin, lath-like crystals. They are transparent and non-fluorescent, with a vitreous, sometimes also pearly, lustre and a white streak having a pale-green cast. Mohs hardness is about 2.5. The crystals are brittle with an irregular fracture; no cleav- age was observed. D(meas.) is 2.95(2) and D(calc.) is 2.907 gcm−3 (for empirical formula, CG). Common associates are brochantite and various other hydrated metal sulfates. Electron-microprobe analyses of the CG material yielded (wt. %) CuO 42.45, CoO 6.58, NiO 3.37, ZnO 3.14, SO3 22.12, and H2O 22.62 (calcu- lated on structural grounds), and total D 100.30 wt. %, giving the empirical formula (based on 20 O atoms) (Co0:63Ni0:32Zn0:28Cu3:83/65:06S1:98O20H18:00. The simplified formula is (Co,Ni)(Cu,Zn)4(SO4/2(OH)6 6H2O, and the endmember formula is CoCu4(SO4/2(OH)6 6H2O. Scanning electron microscopy–energy dispersiveq X-ray spectroscopy (SEM–EDS) analyses of the (Zn-free)q EZ material gave the simplified average formula (Co0:92Ni0:21Mg0:01Cu3:79/64:93(SO4/2:08(OH)6 6H2O. Optically, gobelinite (CG) is biaxial negative, with α D ◦ ◦ 1:576.2/, β D 1:617.2/ and γ D 1:630.2/; 2Vmeasq D 58.4/ and 2Vcalc D 57:5 . Dispersion is weak, r > v; orientation is X D β, Y D γ and Z ≈ α, with strong pleochroism X equaling colourless, Y equaling green and Z equaling pale green. The mineral is monoclinic, space group P 21=c, with a D 5:599.1/, b D 6:084.1/, c D 23:676.5/ Å, β D 95:22.3/◦ and V D 803:2.3/ Å3 (at 100 K; CG) and a D 5:611.1/, b D 6:103.1/, c D 23:808.5/ Å, β D 95:18.3/◦ and V D 811:9.3/ Å3 (at 298 K; EZ), respectively (Z D 2). The eight strongest mea- sured powder X-ray diffraction lines (d in Å (I) hkl (CG material)) are 11.870 (100) 002, 5.924 (40) 004, 4.883 (10) 102, 4.825 (15) 013, 3.946 (15) 006, 2.956 (15) 008, 2.663 (20) 202 and 2.561 (15) 123. Single-crystal structure determinations gave R1 D 0:0310 (CG) and 0.0280 (EZ). The atomic arrangement is based on brucite- like sheets formed from edge-sharing, Jahn–Teller-distorted (4 C 2 coordination) CuO6 octahedra. These sheets are decorated on both sides with SO4 tetrahedra and linked via hydrogen bonds to interstitial, fairly regular Co(H2O)6 octahedra. The name alludes to the Old French word gobelin, equivalent to the German word kobold, from which the designation of the element cobalt was derived. Published by Copernicus Publications on behalf of the European mineralogical societies DMG, SEM, SIMP & SFMC. 638 S. J. Mills et al.: Gobelinite, the Co analogue of ktenasite 1 Introduction mines, removed silver from ore and made it useless (kobold ore), and also made miners sick (Ashliman, 2006). The Cap The secondary hydrated Zn–Cu–sulfate ktenasite was Garonne ores contain Pb and As, which form part of this first described from Lavrion, Greece, by Kokko- folklore. The Eisenzecher Zug mine is poor in Pb and As ros (1950), who suggested the approximate formula but locally rich in Co ores. In order to avoid confusion with (Cu,Zn)3SO4(OH)2 2H2O. Nearly 30 years later, Raade cobaltite and because the Cap Garonne locality is in France, (1977) and Olsen andq Lewis (1979) provided new data on we prefer to honour the Old French roots of the word gobelin. ktenasite from Norway and Colorado, USA, respectively, Type material is preserved in the mineralogical collec- and the crystal structure (monoclinic, P 21=c, a D 5:589.1/, tions of Geosciences, Museums Victoria, GP.O. Box 666, b D 6:166.1/, c D 23:751.7/ Å and β D 95:55.1/◦) was Melbourne, Victoria 3001, Australia, registration number finally published by Mellini and Merlino (1978). They M54565 (Cap Garonne), and the Naturhistorisches Museum, showed that the mineral can be viewed as having the Burgring 7, 1010 Vienna, Austria, registration number O general formula (M1)2.M2)4.M3)4(SO4/4(OH)12 12H2O, 1045 (Eisenzecher Zug). where M1 D Zn, or another minor divalent cation withq near regular octahedral coordination geometry, and with M2 and M3 being sites with more or less Jahn–Teller-distorted 2 Occurrence octahedral coordination geometries, which are occupied by Gobelinite was found by Valérie Galea-Clolus on specimens a mixture of Cu, Zn or other cations. Mellini et al. (1981) from the famous Cap Garonne mine (Favreau and Galea- provided details on the crystal chemistry of ktenasite Clolus, 2014), Var, Provence-Alpes-Côte d’Azur, France and demonstrated that samples have appreciably variable (type locality; 43◦405300 N, 6◦105500 E), the type locality for Zn V Cu ratios but noted that compositions with Cu V Zn 14 other minerals. More specifically, the type specimen of ratios near 1 V 1 are common. They proposed the general gobelinite was collected at pillar 78b in the north mine. Go- formula Zn(Cu Zn /(SO / (OH) 6H O. Recently, x 4−x 4 2 6 2 belinite is restricted to an area of the mine, called “fond de after the approval of the Mg analogue of ktenasite with q mine”, where most of the new species were found at Cap the name fehrite, MgCu .SO / .OH/ 6H O (IMA2018- 4 4 2 6 2 Garonne. Gobelinite has also been found in pillars 78, 79 125a; Schlüter et al., 2020), the ideal formula of ktenasite q and 80. was modified in an executive decision taken by the IMA Gobelinite was also found in 1997 on specimens from Commission on New Minerals, Nomenclature and Classi- the Schlänger und Eichert vein of the Eisenzecher Zug fication (CNMNC) from .Cu;Zn/ .SO / .OH/ 6H O to 5 4 2 6 2 mine (cotype locality; 50◦490900 N, 7◦5901400 E), Eiser- ZnCu .SO / .OH/ 6H O (Miyawaki et al., 2019). 4 4 2 6 2 q feld, Siegerland, North Rhine-Westphalia, Germany, by Jo- Studies of ktenasites from many worldwide localities over q hannes Markus Henrich. The Eisenzecher Zug mine, which the last two decades by the authors and colleagues in Aus- consolidated several older mines, worked on Fe−(Cu−Co) tria and Australia have shown that the crystal chemistry of ores and was the most important mine in the Siegerland min- the mineral is quite variable and that some ktenasite samples ing district (Henrich, 1998). The occurrence of gobelinite actually represent new mineral species, in which Zn may be was restricted to a small, fissure-like area in an adit. In sub- partially or fully replaced by Mg, Co, Ni and Cd (nomencla- sequent years, no additional material could be found. ture proposal in preparation). Originally independent studies of the Co analogue of ktenasite from a French locality (Cap Garonne) and a German locality (Eisenzecher Zug mine), led 3 Appearance and physical properties by the first and second author, respectively, were combined to propose a new mineral species, with the name gobelinite, At Cap Garonne, gobelinite occurs mostly as vitreous to the IMA–CNMNC. Both the mineral and name were ap- crystals, sometimes with a pearly lustre. Their colour is proved in late 2018 (IMA2018–167). The name, pronounced usually pale green and rarely bluish green. No colour zoning (/ /), is in reference to kobold (German), meaning was observed in individual crystals. The crystal size is “goblin”, a superstitious term once used for the ore of cobalt commonly 0.1 to 0.2 mm and rarely up to 0.5 mm in length. by medieval miners. The etymology of both the element The crystals are blocky to thin and lath-like, with sharp cobalt and cobaltite comes from the German word kobold rectangular outlines (Fig. 1). Crystals are elongated on [010] (first used in the 16th century; Pfeifer, 2004), which itself and flattened on f001g. Forms observed are f001g, f031g and originates from the Old French gobelin, used around 1195 in f201g (Fig. 2). The crystals often form in the spaces between Ambroise of Normandy’s Guerre sainte, and Medieval Latin quartz grains, or between quartz pebbles and conglomerate.
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