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Kaznakhtite, Ni6Co3+2(CO3)(OH)16⋅4H2O, a new natural layered double hydroxide, the member of the hydrotalcite supergroup

Published online by Cambridge University Press:  21 July 2022

Anatoly V. Kasatkin*
Affiliation:
Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninsky Prospekt 18-2, 119071 Moscow, Russia
Sergey N. Britvin
Affiliation:
St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Nanomaterials Research Center, Kola Science Center of Russian Academy of Sciences, Fersman Str. 14, 184209 Apatity, Murmansk Region, Russia
Maria G. Krzhizhanovskaya
Affiliation:
St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
Nikita V. Chukanov
Affiliation:
Institute of Problems of Chemical Physics of the Russian Academy of Sciences, 142432 Chernogolovka, Moscow region, Russia
Radek Škoda
Affiliation:
Department of Geological Sciences, Faculty of Science, Masaryk University, Kotlářská 2, 611 37, Brno, Czech Republic
Jörg Göttlicher
Affiliation:
Karlsruhe Institute of Technology, Institute for Synchrotron Radiation, Hermann-von-Helmholtz-Platz 1, D-76344, Eggenstein-Leopoldshafen, Germany
Dmitry I. Belakovskiy
Affiliation:
Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninsky Prospekt 18-2, 119071 Moscow, Russia
Igor V. Pekov
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
Victor V. Levitskiy
Affiliation:
Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninsky Prospekt 18-2, 119071 Moscow, Russia
*
*Author for correspondence: Anatoly V. Kasatkin, Email: anatoly.kasatkin@gmail.com
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Abstract

Kaznakhtite, ideally Ni6Co3+2(CO3)(OH)16⋅4H2O, is a new member of the hydrotalcite group within the hydrotalcite supergroup. The mineral was discovered at the Kaznakhtinskiy ultrabasic massif, Altai Republic, SW Siberia, Russia. It occurs as powdery aggregates forming flattened lenses up to 1.5 × 0.5 cm and veinlets up to 1 cm long and up to 1 mm thick in aggregates of chrysotile, lizardite, stichtite and dolomite. Other associated minerals include brucite, chromite, heazlewoodite, manganochromite, magnetite and magnesioferrite. Kaznakhtite aggregates are composed of tiny platy grains up to 0.01 mm across. Kaznakhtite is light green and translucent in aggregates. It has an earthy lustre and white streak. Cleavage is micaceous on {001}. Dcalc = 2.864 g cm–3. The mineral is optically uniaxial (–) with ɛ = 1.657(3) and ω = 1.676(3), and weakly pleochroic in greenish hues, ω > ɛ. Chemical composition (wt.%, electron microprobe, Co valence state determined by XANES spectroscopy, CO2 and H2O calculated by stoichiometry) is: MgO 2.15, NiO 47.40, ZnO 0.22, Al2O3 0.16, Cr2O3 0.98, Co2O3 17.42, Cl 0.63, CO2 5.05, H2O 24.60, –O=Cl –0.14, total 98.47. The empirical formula calculated based on the sum of all metal cations = 8 apfu is (Ni5.54Mg0.47Zn0.02)Σ6.03(Co3+1.83Cr0.11Al0.03)Σ1.97C1.00O2.99(OH)15.84Cl0.16⋅4H2O. Infrared spectroscopy confirmed the presence of CO32– anions, OH– groups and H2O molecules. The crystal structure was refined by the Rietveld method with RB = 0.19%. Kaznakhtite is trigonal, space group R͞3m, a = 3.0515 (3), c = 23.180 (3) Å, V = 186.93 (4) Å3 and Z = 3/8. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 7.72 (100) (003); 3.863 (24) (006); 2.630 (4) (101); 2.576 (10) (012); 2.294 (6) (015); 1.950 (4) (018); 1.526 (4) (110); and 1.497 (4) (113). Kaznakhtite is a Co3+ analogue of reevesite, Ni6Fe3+2(CO3)(OH)16⋅4H2O. The mineral is named after its type locality.

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Copyright © The Author(s), 2022. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland
Figure 0

Fig. 1. Kaznakhtinskiy massif. The red arrow indicates the exact place where specimens with kaznakhtite were collected. Summer 2019. Photo: V.V. Mukhanov.

Figure 1

Fig. 2. Light green powdery kaznakhtite in fracture of serpentine (composed of intimately intergrown chrysotile and lizardite) with lilac stichtite. Fragment of holotype sample, Fersman Mineralogical Museum registration number 5727/1. Field of view: 3 × 2 cm.

Figure 2

Fig. 3. Aggregates of kaznakhtite (white) in cracks of lizardite serpentinite (grey). Polished section. SEM (BSE) image.

Figure 3

Fig. 4. Powder infrared absorption spectrum of kaznakhtite. Wavenumbers of admixed lizardite are given in parentheses.

Figure 4

Fig. 5. Co K-edge XANES spectra of (1) kaznakhtite, (2) heterogenite Co3+OOH from the Democratic Republic of the Congo, and (3) synthetic Co2+(OH)2.

Figure 5

Fig. 6. Co K-edge XANES spectrum of kaznakhtite (1) and reference spectra for Co(III) [heterogenite CoOOH from the Democratic Republic of the Congo (2)], Co(II,III) [Co3O4 (3)], and Co(II) [Co(OH)2 (4), CoSO4 (5), and CoCO3 (6)] compounds.

Figure 6

Table 1. Chemical composition of kaznakhtite (wt.%).

Figure 7

Fig. 7. Rietveld refinement plot of kaznakhtite sample with 22% lizardite-2H1 impurity.

Figure 8

Table 2. Powder X-ray diffraction data (d in Å) for kaznakhtite and its synthetic analogue

Figure 9

Fig. 8. Crystal structure of kaznakhtite. (a) General view of the structure approximately parallel to the c axis. The 3R stacking of the interleaving brucite-like and carbonate layers. (b) Projection of carbonate layer onto {001}. The CO3 group is split into six possible symmetrically equivalent positions. Legend: M site (octahedral cations) – pale-green; C – grey; O – red.

Figure 10

Table 3. Crystal parameters and Rietveld refinement details for kaznakhtite.

Figure 11

Table 4. Fractional atomic coordinates and isotropic displacement parameters (Biso, Å2) for kaznakhtite.

Figure 12

Table 5. Selected bond lengths (Å) in the crystal structure of kaznakhtite.

Figure 13

Table 6. Comparative data for kaznakhtite, reevesite, takovite and comblainite.

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