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Articles |
1 Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region, 142432, Russia, e-mail: chukanov{at}icp.ac.ru
2 Department of Mineralogy, Faculty of Geology, Moscow State University, Vorobievy Gory, Moscow, 119899, Russia
3 Institute of Mineralogy, Geochemistry, and Crystal Chemistry of Rare Elements, Russian Academy of Sciences, Veresaev str., 15, Moscow, 121357, Russia
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Key-words: labuntsovite group, nomenclature, labuntsovite, nenadkevichite, korobitsynite, vuoriyarvite, lemmleinite, kuzmenkoite, organovaite, paralabuntsovite, tsepinite, karupmöllerite, gutkovaite.
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Introduction |
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Although more than sixty papers have been published so far on the mineralogy and crystal chemistry of labuntsovite and related species, the proliferating terminology became rather confusing. For example, the name "nenadkevichite" has been applied to orthorhombic and monoclinic members, as well as to minerals with Ti > Nb or Nb > Ti, and to minerals with Na > K or K > Na (Perrault et al., 1973; Organova et al., 1981; Rastsvetaeva et al., 1994).
The evident need to clarify the nomenclature of these minerals prompted us to undertake a comprehensive investigation. This included the determination of the chemical compositions of more than 300 specimens (from 12 different massifs) by electron microprobe analysis. The results show remarkably wide ranges of the species-forming components (weight %): Na2O 0.17–13.87, K2O 0–14.90, CaO 0–7.28, SrO 0–8.24, BaO 0–16.90, MgO 0–2.29, MnO 0–7.37, FeO 0–4.96, ZnO 0–7.06, TiO2 0.81–27.10, Nb2O5 0.14–38.89. Additionally, there are also variations of physical properties, IR spectra and crystal structures between the members of the group. Single-crystal structure analysis has been performed for a number of LG minerals with unusual physical properties and/or chemical compositions (Rastsvetaeva et al., 1994, 1996, 1997a, 1997b, 1998, 2000a, 2000b, 2001; Golovina et al., 1998). The results obtained in the above cited works demonstrate the existence of a number of structural types within the LG.
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Crystal structure |
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7.4, b 14.2, c 7.1 Å; Fig. 3). Both A cation sites are relatively small and similar in size, so they are occupied mainly by Na. The general formula is: A6M4(T4O12)2(O,OH)4 ·nH2O (Z = 1); T = Si; A = Na, 
; M = Nb (nenadkevichite) or Ti (korobitsynite). The presence of vacancies up to 50 % is characteristic of the A sites. Minor amounts of larger cations can be present: a structurally investigated nenadkevichite (Perrault et al., 1973) contained 0.24 K atoms and 0.11 Ca atoms per unit cell.
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14.3, b 13.8, c 7.75 Å, ±, 117°; see Table 1) are the commonest and best studied monoclinic structures (Golovastikov, 1973; Organova et al., 1976, 1981; Rastsvetaeva et al., 1996, 1997b, 1998). In this structure type, an additional octahedral position is located at the site where the distance between chains is minimal; this site is called "the linking octahedron" D and is distinct from the M octahedra present in the chains. Three non-equivalent, extra-framework cation sites (A, B, and C) are present in this structural type, and the general formula is: A4B4C4D2M8(T4O12)4 (OH,O)8 ·nH2O (Z=1). The cations in the sites are: T = Si; M = Ti, Nb; D = small bivalent cations (M2+) such as Mn, Fe, Mg, Zn; A = Na; B = K, sometimes with minor Na; C = Ba, K. The distance between the sites C and D is short (
2.1 Å) and cations cannot occur in both sites at the same time. If the D site is occupied by cations, H2O molecules occur in C and complete the octahedral coordination of the D cations; if D = , C can contain cations. The following mechanism governs the occupancy of C and D sites:
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3. Kuzmenkoite-type structure (space group C2/m, a 14.4, b 13.9, c 7.8 Å, β 117°) differs from that of labuntsovite by the absence of the A cations. The B site is occupied mainly by K, and the C site is cation-deficient (Golovina et al., 1998). Splitting of the B site can lower the symmetry to Cm (Rastsvetaeva et al., 2000b). The idealized formula for the minerals with kuzmenkoite structure is: K4D2M8(Si4O12)4(OH,O)8 ·nH2O (Z = 1; n = 10–12). Two minerals, kuzmenkoite-Mn with D = Mn2+, M = Ti, and kuzmenkoite-Zn with D = Zn2+, M = Ti have been described to date (Chukanov et al., 1999b; Chukanov et al., in press). A new mineral karupmöllerite-Ca (see Table 2) is related to kuzmenkoite; it can be considered as B-vacant and Nb-dominant analog of hypothetical "kuzmenkoite-Ca".
4. In the organovaite-type structure (space group C2/m, a 14.5, b 14.0, c 15.7 Å, β = 118°), the c parameter is doubled, due to the splitting of the K site. Two Nb-dominant members, organovaite-Mn (Chukanov et al., 2001b) and organovaite-Zn (Pekov et al., in press) and one Ti-dominant member, parakuzmenkoite-Fe (Chukanov et al., 2001c) are known in this subgroup. The common formula is: K4D2M8(Si4O12)4(OH,O)8 ·nH2O (Z = 2; n = 12–14).
5. Vuoriyarvite-type structure. This structural type (Rastsvetaeva et al., 1994) is characterized by the space group Cm (a 14.7, b 14.2, c 7.9 Å, β 118°) and numerous split sub-sites. The Vuoriyarvite-K structure contains four sub-sites partly occupied by K, three sub-sites by Na, and five sub-sites by H2O (Rastsvetaeva et al., 1994). The general formula is: A12-x2M8(Si4O12)4(OH,O)8·nH2O (Z = 1) where M = Nb, Ti; the linking D octahedron is absent; "A" denotes the total combination of sub-sites of extra-framework cations similar to those in zeolites; n= 12–16. Tsepinite-Na, a new species, is a Ti- and Na-dominant analogue of vuoriyarvite-K (Rastsvetaeva et al., 2000a; Shlyukova et al., 2001).
6. Unlike labuntsovite-type structure, in the gutkovaite-type structure the A site is split into two non-equivalent sites A1 and A2; as a result, the symmetry is lowered to Cm. In gutkovaite-Mn (Pekov et al., in press) in A1 prevails Ca, A2 is vacant, D is occupied by Mn.
The occupancy of D and C by a competitive mechanism (1) is an important feature of the monoclinic LG mineral structures. The already stated site occupancy, is clearly correlated with compositional features. Separation of high-valent and bivalent octahedral cations between M and D sites has been reliably confirmed (Chukanov et al., 1999b). In particular, the correlation on Fig. 4 demonstrates that the number of D cations per Si16 varies continuously from 0 to 2.
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The nomenclature of monoclinic LG minerals is based on the following principles and is in accordance with the rules recommended by IMA CNMMN (Nickel & Grice, 1998):
The first and principal rule for species distinction is the 50 % rule. However, a serious problem is represented by the important role of vacancies in the D octahedron and extra-framework cation sites. Therefore, a second important rule is: if a site is more than 50% occupied by cations (i.e. 
cations > ), the component which predominates over any other must be considered as a species-forming cation. This is similar to Levinson's rule: if the sum of REE prevails over any other component in this site, the mineral is considered as a rare-earth species and the prevailing REE is used to suffix the root name of the mineral species. If the site is less than 50 % occupied with cations (i.e. cations < , H2O), this site is considered cation-deficient. Full occupancy of D site per 16Si is 2 atoms, and that of C site is 4 atoms, therefore the 50 % threshold is 1 atom per formula unit for D cations and 2 atoms per formula unit for C cations. Only cations, not water molecules, are taken into account in the C site. Using the last rule, we can identify mineral species on the basis of cation composition (e.g. from electron microprobe analysis).
In spite of the zeolite-like character of structurally ordered LG minerals (members with space groups C2/m and I2/m), all extra-framework cations occupy only two or three fixed, non-split positions. Furthermore, the occupancies obtained from structure analysis are in good agreement with real chemical compositions. Mineral species within the corresponding series are distinguished by root-names (to distinguish the cases Ti > Nb and Ti < Nb) and by modifiers denoting the most abundant cation in the species-forming, i.e. non-vacant, C or D position. An analogue of labuntsovite has been described with vacancies predominating in both C and D positions (Bulakh & Evdokimov, 1973; Organova et al., 1981). For this mineral, the name "labuntsovite-" (not an approved name) could be used.
In vuoriyarvite, we observe a condition close to that existing in zeolites: extra-framework cations are situated in numerous split sites (sub-sites) dominated by vacancies. For this reason, mineral species with vuoriyarvite-like structures are distinguished by the prevailing extra-frame-vork cation (without distinction of extra-framework sites), in a similar way to the accepted rules for zeolites (Coombs et al., 1997) - see Table 1.
Non-approved and obsolete names for the labuntsovite-group minerals
The complex and variable chemical composition of the LG minerals and the similarity of their physical properties has resulted in the unnecessary proliferation of names, mainly derivatives of the "old" mineral names, labuntsovite and nenadkevichite. These non-approved and obsolete names are given here in italic type, with their corresponding accepted mineral species names under the present nomenclature.
Titanium elpidite, titano-elpidite (Labuntsov, 1926) = labuntsovite-Mn.
Labuntsovite I (Organova et al., 1981), according to the new nomenclature rules it should be named labuntsovite-.
Potassium labuntsovite, labuntsovite II (Organova et al., 1981) = labuntsovite-Mn.
Labuntsovite III (Organova et al., 1981), described also as Potassium-rich labuntsovite (Rastsvetaeva et al., 1998) = lemmleinite-K.
Monoclinic nenadkevichite, Ti-nenadkevichite (Organova et al., 1976) = monoclinic member of LG with Ca as the most abundant D-cation (not approved yet).
K-rich nenadkevichite (Rastsvetaeva et al., 1994) = vuoriyarvite-K.
K-dominant nenadkevichite (Petersen et al., 1996) = vuoriyarvite-K?
According to the accepted nomenclature, the old names "vuoriyarvite", "lemmleinite" and "kuzmenkoite" must be replaced with vuoriyarvite-K, lemmleinite-K and kuzmenkoite-Mn, respectively. The name "labuntsovite" has been applied to different minerals: labuntsovite-Mn (Semenov & Burova, 1955; Golovastikov, 1973; partly: Bulakh & Evdokimov, 1973; Organova et al., 1981), labuntsovite-Mg (partly: Bulakh & Evdokimov, 1973), labuntsovite- (partly: Bulakh & Evdokimov, 1973; Organova et al., 1981), lemmleinite-K (partly: Organova et al., 1981), paralabuntsovite-Mg (Milton et al., 1958).
Labuntsovite was first described in 1926 from the Khibiny massif, Kola, as "titanium elpidite" (Labuntsov, 1926). In 1955, the same mineral from the Lovozero massif, Kola, was studied and named "labuntsovite" (Semenov & Burova, 1955). We have examined both type specimens by electron microprobe analysis: Semenov's holotype of labuntsovite from Kuftn'yun Mt., Lovozero massif, and Labuntsov's "titano-elpidite" type specimen from Yum'egor Pass, Khibiny massif, which are deposited in the Fersman Mineralogical Museum, Moscow (samples ## 62556 and 41097 respectively). Both samples are labuntsovite-Mn in accordance with the accepted nomenclature. Their empirical formulae are:
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Rules for the calculation of crystal chemical formulae for structurally ordered monoclinic labuntsovite-group minerals (labuntsovite, lemmleinite, kuzmenkoite and paralabuntsovite subgroups)
In comparison to orthorhombic members, monoclinic LG minerals are characterized by more complicated and widely variable chemical compositions. It is necessary to take into consideration some important crystal chemical features of these minerals for the correct calculation of their formulae. The scheme of calculation given below for phases with labuntsovite structure is based on the following structure features:
2.1 Å), and the mechanism of their cation occupancy is as discussed above. Taking into account the structural data, we propose the following scheme of calculation for the crystal chemical formulae of LG minerals with space groups C2/m and I2/m:
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Received 6 December 2000
Modified version received 30 April 2001
Accepted 3 September 2001
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References |
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Chukanov, N.V., Pekov, I.V., Golovina, N.I., Zadov, A.E., Nedel'ko, V.V. (1999a): Kuzmenkoite, K2(Mn,Fe)(Ti,Nb)4[Si4O12]2 (OH)4·5H2O, a new mineral. Zapiski VMO, 4, 42–50 (in Russ.).
Chukanov, N.V., Pekov, I.V., Rastsvetaeva, R.K., Nekrasov, A.N. (1999b): Labuntsovite: solid solutions and features of the crystal structure. Can. Mineral., 37, 901–910.
Chukanov, N.V., Pekov, I.V., Rastsvetaeva, R.K., Zadov, A.E., Nedelko, V.V. (2001a): Lemmleinite-Ba, Na2K2Ba1+xTi4[Si4O12]2 (O,OH)4 ·5H2O, a new mineral of labuntsovite group. Zapiski VMO, 3, 36–43 (in Russ.).
Chukanov, N.V., Pekov, I.V., Semenov E.I., Zadov, A.E., Krivovichev, S.V., Burns, P.C. (2001c, in press): Parakuzmenkoite-Fe, (K,Ba)2Fe(Ti,Nb)4[Si4O12]2(O,OH)4 ·7H2O, a new labuntsovite group mineral. Zapiski VMO, 6 (in Russ.).
Chukanov, N.V., Pekov, I.V., Zadov, A.E., Azarova, Yu. V., Semenov, E. I. (in press): Kuzmenkoite-Zn, K2Zn(Ti,Nb)4(Si4O12)2 (OH,O)4 
6–8H2O, a new mineral of the labuntsovite group from Lovozero massif, Kola peninsula. Zapiski VMO (in Russ.).
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Khomyakov, A.P., Nechelyustov, G.N., Ferraris, G., Gula, A., Ivaldi, G. (2001): Labuntsovite-Fe and labuntsovite-Mg - two new minerals from the Khibina and Kovdor alkaline massifs, Kola peninsula. Zapiski VMO, 4, 36–45 (in Russ.).
Khomyakov, A.P., Nechelyustov, G.N., Rastsvetaeva, R.K., Dorokhova, G.I. (1999): Lemmleinite, NaK2(Ti,Nb)2Si4O12 (O,OH)2·2H2O, a new mineral of the labuntsovite-nenadkevichite family. Zapiski VMO, 5, 54–63 (in Russ.).
Kuz'menko, M.V. & Kazakova, M.E. (1955): Nenadkevichite, a new mineral. Doklady AN SSSR, 100, 1159–1160 (in Russ.).
Labuntsov, A.N. (1926): Titanium elpidite from the Khibiny Tundras and its paragenesis. Doklady AN SSSR, ser. A, 39–42 (in Russ.).
Milton, Ch., Mrose, M.E., Fahey, J.J., Chao, E.C.T. (1958): Labuntsovite from the Trona Mine, Sweetwater County, Wyoming. Bull. Geol. Soc. Amer., 69, 1614–1621.[GeoRef]
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Organova, N.I., Shlyukova, Z.V., Zabavnikova, N.I., Platonov, A.N., Rudnitskaya, E.S. (1976): On crystal chemistry of labuntsovite and nenadkevichite. Izvestiya AN SSSR, ser. geol., 2, 98–116 (in Russ.).
Pekov, I.V., Chukanov, N.V., Khomyakov, A.P., Rastsvetaeva, R.K., Kucherinenko, Ya.V., Nedel'ko, V.V. (1999): Korobitsynite, Na3-x(Ti,Nb)2[Si4O12](OH,O)2 ·3–4H2O, a new mineral from Lovozero massif, Kola Peninsula. Zapiski VMO, 3, 72–79 (in Russ.).
Pekov, I.V., Chukanov, N.V., Rastsvetaeva, R.K, Zadov, A.E., Kononkova, N.N. (in press): Gutkovaite-Mn, CaK2Mn(Ti,Nb)4 (Si4O12)2(O,OH)4 •5H2O, a new mineral of the labuntsovite group from Khibiny massif, Kola peninsula. Zapiski VMO (in Russ.).
Pekov, I.V., Chukanov, N.V., Zadov, A.E., Krivovichev, S.V., Azarova, Yu.V., Burns, P.C., Schneider, J. (2001, in press): Organovaite-Zn, K2Zn(Nb,Ti)4(Si4O12)2(O,OH)4 ·6H2O, a new mineral of the labuntsovite group. Zapiski VMO, 6 (in Russ.).
Perrault, G., Boucher, C., Vicat, J., Cannillo, E., Rossi, G. (1973): Structure cristalline du Nenadkevichite (Na,K)2-x(Nb,Ti)(O,OH) (Si2O6) ·2H2O. Acta Cryst. 29, 1432–1438.[CrossRef]
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Rastsvetaeva, R.K., Arakcheeva, A.V., Khomyakov, A.P. (1996): Crystal structure and microtwinning of a new monoclinic analogue of nenadkevichite. Doklady RAN, 351, 207–211 (in Russ.).
Rastsvetaeva, R.K., Chukanov, N.V., Pekov, I.V. (1997a): Crystal structure of a new mineral, titanium analogue of orthorhombic nenadkevichite. Doklady RAN, 357, 364–367 (in Russ.).
Rastsvetaeva, R.K., Chukanov, N.V., Pekov, I.V. (1997b): Crystal structure of analogue of labuntsovite with high ordering of potassium and barium. Doklady RAN, 357, 64–67 (in Russ.).
Rastsvetaeva, R.K., Chukanov, N.V., Pekov, I.V. (2000b): Refined crystal structure of kuzmenkoite. Kristallografiya, 45, 830–832 (in Russ.).
Rastsvetaeva, R.K., Chukanov, N.V., Pekov, I.V., Shlyukova, Z.V., Khomyakov, A.P. (1998): Crystal structures of two potassium-rich labuntsovites and crystal chemistry of labuntsovite-nenadke-vichite family minerals. Kristallografiya, 43, 874–881 (in Russ.).[GeoRef]
Rastsvetaeva, R.K., Organova, N.I., Rozhdestvenskaya, I.V., Shlyukova, Z.V., Chukanov, N.V. (2000a): Crystal structure of hydronium bearing labuntsovite group mineral from Khibiny massif. Doklady RAN, 371, 336–340 (in Russ.).
Rastsvetaeva, R.K., Pekov I.V., Nekrasov Yu.V. (2001): Crystal structure and microtwinning of Ca-rich analog of labuntsovite. Kristallografiya, 46, 415–417 (in Russ.).
Rastsvetaeva, R.K., Tamazyan, R.A., Pushcharovsky, D.Yu., Nadezhina, T.N. (1994): Crystal structure and microtwinning of K-rich nenadkevichite. Eur. J. Mineral., 6, 5O3–509.
Semenov, E.I. Burova, T.A. (1955): On a new mineral, labuntsovite, and so-called titanoelpidite. Doklady AN SSSR, 101, 1113–1116 (in Russ.).
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Shlyukova, Z.V., Chukanov N.V., Pekov, I.V., Rastsvetaeva, R.K., Organova, N.I., Zadov, A.B. (2001): Tsepinite-Na (Na,H3O,K,Sr,Ba)2(Ti,Nb)2[Si4O12](OH,O)2·3H2O, a new mineral of the labuntsovite group. Zapiski VMO, 3, 43–50 (in Russ.).
Subbotin, V.V., Voloshin, A.V., Pakhomovskii, Ya.A., Bakhchisaraytsev, A.Yu., Pushcharovsky, D.Yu., Rastsvetaeva, R.K., Nadezhina, T.N. (1998): Vuoriyarvite, (K,Na)2(Nb,Ti)2Si4O12(O,OH)2 •4H2O, a new mineral from carbonatites of Vuoriyarvi, Kola Peninsula. Doklady RAN, 358, 4, 517–519 (in Russ.).
Yamnova, N.A., Pekov I.V., Kabalov Yu.K., Schneider Yu., Chukanov N. V. (2000): Crystal structure of a new representative of the labuntsovite group. Doklady RAN, 375, 4, 487–490 (in Russ.).
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