NEW DATA on BETALOMONOSOVITE Boris Ye

New Data on Minerals. 2014. Vol. 49 23

NEW DATA ON BETALOMONOSOVITE Boris Ye. Borutzky Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, [email protected] Olga A. Ageeva, Oksana V. Karimova, Pavel M. Kartashov Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry (IGEM), Russian Academy of Sciences, Moscow, [email protected] Olga V. Yakubovich Moscow State University, Geological Faculty, Moscow, [email protected]

The new data on compositional variations, refined crystal structure, thermal properties, and formation conditions of betalomonosovite are discussed. The results obtained assert that betalomonosovite differs from lomonosovite with which the former is identified. It has individual chemical and structural features, and distinct geological and genetic setting, and should be rehabilitated as individual mineral species. 3 tables, 6 figures, 58 references. Keywords: lomonosovite, betalomonosovite, murmanite, crystal structure, Khibiny massif, melteigite-urtite, juvite, rischorrite, hyperagpaitic minerals assemblage.

The aim of this study is comparison of new (1950) was studied in detail by Es'ko va (1976), data on betalomonosovite, Na4Ti4(Si2O7)2 (O,F)4 Vlasov et al. (1959), and Semenov et al. (1961). · Na2H4(PO4)2 results of investigation of lomo- In contrast to murmanite, this mineral con- · nosovite Na4Ti4 (Si2O7)2(O,F)4 Na6(PO4)2, with tained P and was anhydrous Na4Ti4Si4(O,F)18 · which betalomonosovite is identified accor- 2Na3PO4. In Khibiny, Dorfman (1962) found ding to recommendation of the Commission lomonosovite for the first time in the district of on new Minerals and Mineral Names Interna - apatite deposits. tional Mineralogical Association in 1988, and Betalomonosovite discussed in this article, · those of murmanite Na4Ti4(Si2O7)2O4 (H2O)4 was found and described as mineral no. 2 in as final product of supergene alteration of 1938 by Gerasimovsky, but its detailed exami- lomonosovite, with which betalomonosovite is nation was started in 1960s (Gerasimovsky unreasonably attributed to the same solid so - and Kazakova, 1962), when Semenov et al. lution series as intermediate species of similar (1961) found more representative material in alteration. We do not discuss other lomonoso- the same district. In Khibiny, betalomonosovite group minerals: vuonnemite and episto- vite was found at the Rasvumchorr deposit in lite, Nb analogs of lomonosovite and murma - 1958 (Sokolova, 1961; Sokolova et al., 19712). nite, respectively, and quadruphite, sobole- In contrast to the previous findings, this mi - vite, and polyphite, Ca-and Mn-rich analogs neral contained P and significant amount of of lomonosovite, although they are end-mem- water; betalomonosovite1 was described by · bers of probable solid solution series for iso- the following formulae: Na4Ti4 Si4(O,F)18 (Na,H)6 · · morphic admixtures typical of betalomonoso- (PO4)2, Na4Ti4Si4(O,F)18 Na2HPO4 NaH2PO4 or · vite and could be formed in similar geological Na4Ti4Si4(O,F)18 Na3[PO4(OH)PO2(OH)2]. To environment. date, it is reasonably chemical, structural, and geological characterized in the context of its Discovery nature, abundance in alkaline rocks of ag - paitic nepheline syenite massifs and forma- In 1890, Wilhelm Ramsay described new tion conditions to regard it as individual mi - hydrous niobo-titano-silicate, mineral no. 3 neral species. Nevertheless, it was missinlcu - (Ramsay, 1890) from the Lovozero tundras. In ded by CNMMN IMA into the list of dis cre - 1923, members of the Fersman expedition dited minerals (Nickel and Mandarino, 1988) found this mineral in the same district and that hampers its further detailed study. This described it as violophillite. After detailed forced us to carry out the new measurement of exa mination, Gutkova (1930) renamed it to the chemical composition and crystal struc- mur manite with the refined composition Na4Ti4 ture of betalomonosovite, as well as, its gene - · Si4O18 4H2O (Minerals…, 1937). Lomo no so - tic relationship with lomonosovite and mur- vite, anhydrous analog of murmanite, discov- manite to additionally argue the reinstate- ered from the same massif by Gerasi movsky ment of this term. 1 – Many researchers assumed that this name is poor because betalomonosovite is not structural modification of lomonosovite, i.e., b-species (b-lomonosovite), otherwise, term a-lomonosovite should be introduced. 24 New Data on Minerals. 2014. Vol. 49

Geological setting and manite were established to be common in the formation conditions of murmanite, same rocks: leucocratic varieties of rocks from lomonosovite, and betalomonosovite the differentiated complex (III) with greater amount in foyaite than urtite and lujavrite; Murmanite. Murmanite is abundant ac - leucocratic lujavrite of the lujavrite complex cessory mineral of some peralkaline leuco- (IV), sodalite varieties of poikilitic nepheline- cratic rocks and hosted pegmatites in the sodalite syenite (II), and pegmatites hosted in Lovozero tundras. It was found at Mts. Pun - these rocks. Fresh lomonosovite was observed karuaiv, Suoluaiv, Ninchurt, and Mannepahk; in drill core below 250–300 m, whereas at the cirques Raslak, Sengischorr, and Angvun - depth of 100–200 m below surface it was fol- dasschorr; and in the Chinglusuai, Motchi - lowed by the yellow and violet-pink variety; at suai, and Muruai valleys (Minerals…, 1937). the surface murmanite is pink. Relics of al - According to Bussen and Sakharov (1972) re - tered lomonosovite retaining morphology and ferring to Gutkova (1930) and Es'kova (1959), optical orientation were observed everywhere it occurs as lenticular clusters within layers in murmanite. In other words, it was proved by I-1 and II-2 hosted in juvite, foyaite, and urtite direct methods that murmanite is secondary of the differentiated lujavrite-foyaite-urtite after lomonosovite. complex (complex III); this mineral is com- Experiments in Na and P desalination from mon in leucocratic varieties of lujavrite comp - lomonosovite using hot and cold distillated lex (complex IV) where it forms phenocrysts water performed by Gerasimovsky and Bor - in near-contact porphyry lujavrite (tinguaite) neman-Starynkevich (Borneman-Staryn ke vich, and always occurs in porphyry murmanite 1946) and specified by Zabavnikova (1967) and lujavrite (complex V). Through all rocks, mur- Sokolova et al. (1973) using chemical and ther- manite is observed with lomonosovite typical- mal analysis, and X-ray diffraction supported ly associated with agpaitic minerals: K,Na the probable formation of murmanite by this feldspar, nepheline, sodalite, aegirine, lam- manner. It was established that pink-lilac color prophyllite, and eudialyte. Pegmatite with of murmanite with characteristic absorption murmanite and lomonosovite were also hos - bands at 12650, 18850, and 20600 cm 1 is ted in porphyritic and poikilitic nepheline- caused by Mn3+ (Platonov, 1976) that is also sodalite syenite and tavite (complex II) (Mine - consistent with oxidative environment in mur- rals…, 1937). manite formation. In contrast to Lovozero, in Khibiny, negli- By the further investigations of Kho mya - gible amount of altered murmanite was found kov (1990), it has become clear that in addi- only on the surface (Gutkova, 1930; Kuplet - tion to the lomonosovite – murmanite pair, sky, 1930; 1932; Minerals…, 1937; Dorfman, there are some primary minerals, which are 1962; Tikhonenkov, 1963). Fresh murmanite transformed to the secondary species due to was identified in mines at the Rasvumchorr, Na desalination and hydration as a result of Kukisvumchorr, and Yukspor apatite deposits sharply evolved alkalinity of mineral-forming in pegmatites hosted in coarse-grained urtite medium; these minerals common close to sur- and rischorrite hosting ore sequence, as well face as rule are: vuonnemite, Na11TiNb2Si4 · as, in melteigite of the upper contact zone, P2O25F ® epistolite, Na5TiNb2Si4O17F 4H2O, where it replaces lomonosovite lamellae (So - parakeldyshite, Na2ZrSi2O7 ® keldyshite, ko lova, 1965; Sokolova et al., 1973). The fres - Na3HZr2(Si2O7)2, zirsinalite, Na6CaZrSi6O18 ® hest pinkish white fine-flake murmanite with lovozerite, Na3CaZrSi6O15(OH)3, kazakovite, nacreous luster that could be assumed as Na6MnTiSi6O18 ® tisinalite, Na3MnTiSi6O15 newly formed phase was found as thin (up to (OH)3. They are regarded as individual mine - 1 mm in thickness) stringer cutting massive ral species or varieties with prefix "hydro", for urtite at the Rasvumchorr deposit (Mine ra - example, delhayelite, K3Na2Ca2Si7AlO19(F,Cl)2 · logy…, 1978). ® hydrodelhayelite, KCaSi7AlO17(OH)2 6H2O. Murmanite (associated with lomonosovite) Cogenetic minerals typically associated was found in the same situation from agpaitic with lomonosovite and murmanite are the sa - rocks of the Ilimaussaq massif, South Gre - me: microcline, nepheline, arfvedsonite, and enland (Karup-Mшller, 1983; 1986). sodalite. Lomonosovite inclusions are obser- Lomonosovite. Es'kova (1959) studied in ved in albite, sodalite, cancrinite, ussingite, detail the geological setting of lomonosovite and natrolite; however these inclusions are in the Lovozero massif taking into account the transformed to murmanite only in natrolite. data of Gerasimovsky (1950) and Borneman- This not contradicts the pseudomorphous ori- Starynkevich (1946). Lomonosovite and mur- gin of murmanite and it is clear that meteoric New data on betalomonosovite 25

water or low-hydrothermal fluid is required to et al., 19712). Sufficiently large well-shaped form it. Villiaumite is a guide mineral for betalomonosovite crystals up to 5 mm in size lomonosovite. measured with goniometer by T.A. Yakov lev - In Khibiny, lomonosovite found in slightly skaya were recovered from gisengerite (Soko - different environment from that in Lovozero lova et al., 19712; Mineralogy..., 1978). (Dorfman, 1962; Dudkin, 1959; Dudkin et al., Ageeva and Borutzky (1997) and Ageeva

1959; Sokolova et al., 19711, 1973; Minera - (1999, 2002) studied in detail the relationship logy... 1978) was identified in pegmatites cut- between lomonosovite, betalomonosovite, ting fine-grained trachitoid ijolite-urtite- and murmanite occurred as accessory mine - melteigite, but in the first place in pegmatites rals in the parental rocks of the Khibiny mas- hosted in massive coarse-grained urtite, apa - sif. It was established that accessory lomono- tite-nepheline sequence, and rischorrite at the so vi te is common only in massive coarse-grai - Yukspor, Kukisvumchorr, and Rasvumchorr ned urtite, feldspar urtite, juvite, pyroxene deposits. Lomonosovite is the most typical of rischorrite, and malignite, i.e., in the rocks of aegirine-diopside – feldspar (microcline, adu - Central Arc of the massif and has different laria-like orthoclase) pegmatite, where it is chemical composition and morphology. In ur - associated with nepheline, lamprophyllite, tite, it occurs as the largest (5–10 mm) grains delhayelite, and villiaumite. It is unknown enriched in Na, which are along with pyro- from aegirine-diopside – nepheline pegmati - xene, lamprophyllite, and aenigmatite forms tes depleted in feldspar or feldspar-free. Lo - poikilitic metacrysts enclosing euhedral ne- mo nosovite is associated with microcline, pheline grains (Fig. 1a). Clear smooth bound- aegirine, lamprophyllite, shcherbakovite, and aries between lomonosovite and nepheline lovozerite in pegmatites hosted in rischorrite indicating simultaneous formation of these at the top of apatite body in the Apatite cirque minerals attract attention. As K content inc - of Mt. Rasvumchorr. rea ses from urtite to feldspar urtite, juvite, and These pegmatites are opened by mines at rischorrite, lomonosovite is depleted in Na up the significant depth below surface and deep- to the composition typical of betalomonoso- seated weathering profiles that favors to re- vite and its forms resulted from orthoclase taining fresh lomonosovite. It is murmanitized corrosion become more frequent (Fig. 1b). only along fractures cutting plates. However, In other words, as previously reported for lomonosovite plates occurred in dumps for a pegmatites (Sokolova et al., 19712), betalomo - long period or in pegmatites opened in open nosovite is the most characteristic of rischor- pit are altered to the greater extent up to pin - rite and could be resulted from the transfor - kish violet murmanite. In contrast to Lovoze - ma tion of lomonosovite as primary mineral of ro, lomonosovite or replacing murmanite were massive coarse-grained urtite during rischor- found only in melteigite-urtite of the Central ritization. It should be emphasized once more Arc of the Khibiny massif; they were not iden- that in this process with partial removal of Na tified in nepheline syenite (foyaite, khibinite) and dehydration, unlike murmanitization of rimming the arc. lomonosovite, phosphorous is not removed Betalomonosovite. Betalomonosovite is less and the Ti:Si:P ratio remains constant. Altered frequent mineral as compared with lomo no - lomonosovite is observed in thin sections and sovite and murmanite. In the Lovozero massif, attested by the electron microprobe measure- it was identified in association with micro- ment of Na and P. The alteration is usual in cline, aegirine, arfvedsonite, sodalite, zeo- colorless crystal rims, whereas in the cores lites, eudialyte, lorenzenite (ramsayite), lam - relict light brown-violet lomonosovite is re - pro phyllite, neptunite, and steenstrupine in tained (Fig. 1c). poikilitic nepheline-sodalite syenite and hos - Non-leached phosphorous indicates that ted pegmatites on the right bank of the Tul - this process differs from supergene of low- bn’yunuai river (Semenov et al., 1961; Gerasi - temperature hydrothermal transformation of movsky and Kazakova, 1962). In the Khibiny lomonosovite to murmanite. The review of massif, betalomonosovite was found in associ- mineral assemblages containing betalomo no - ation with microcline, arfvedsonite, lampro- sovite (K-rich adularia-like orthoclase, ne - phyllite, shcherbakovite, wadeite, lovozerite, pheline enriched in K, kalsilite, eudialyte en - and hisingerite as characteristic mineral of riched in K, wadeite, barium lamprophyllite, thin pegmatite veinlets cutting rischorrite at shcherbakovite) shows that it was most likely the top of apatite-nepheline body and in host formed at one of the stages of melteigite-urtite rischorrite of the Apatite cirque at the Ras - fenitization under effect of fluids derived from vumchorr deposit (Sokolova, 1961; Sokolova nepheline syenite magma, i.e., K,Si metaso- 26 New Data on Minerals. 2014. Vol. 49

Fig. 1. Micrographs of accessory lomonosovite and betalomonosovite grains in the rocks of the urtite-juvite-rischorrite complex in the Khibiny massif: (a) poikilitic grains of lomonosovite (Lm) with euhedral nepheline phenocryst (Ne) in massive coarse-grained urtite, plane-polarized light, grain size 2 × 3 mm; (b) newly formed grain of betalomonosovite (b-Lm) corroded by adularia-like orthoclase (Or) on nepheline phenocryst (Ne) in rischorrite, plane-polarized light, grain size 0.4 × 0.8 mm; (c) lomonosovite relics (Lm) in betalomonosovite (b-Lm) in orthoclase form rischorrite, plane-polarized light, grain size 2 × 3 mm. matic alteration affected primary relict rocks perfect metacrysts overgrowing nephe line of Central Arc of the massif and causing the inclusions within adularia-orthoclase poikilitic formation of high- and hyper-potassium rocks crystals associated with potassium titano- and (juvite, rischorrite). The absence or low con- zirconosilicates: astrophyllite, wa deite, delhay - tent of K in betalomonosovite is caused by elite, yuksporite, and phena cite (Fig. 2) are that the incorporation of large K cations into abun dant. In contrast to pseudomorphous be - the mineral crystal structure is impossible or ta lomonosovite, the crystals are colorless, optic strictly limited. angle decreases from 45–55° to 27–36° (So-

The metasomatic hypothesis of rischorrite kolova et al., 19712; Ageeva, 1999). We believe (poikilitic nepheline syenite) origin in the that this undoubtedly indicates physicochemi- Khi biny massif proposed and progressively cal equilibrium at the late stage of rischorritiza- advanced by Solodovnikova (1959), Tikho- tion, presence of individual stability field of nen kov (1963), Rudenko (1964), Titov et al. betalomonosovite differed from that of lomo - (1971), Mineralogy (1978), and Zotov (1989) is nosovite that is basis for its definition as miner- the most probable and elaborated because it is al species or equivalent variety. based on the additional results of detailed study of rock-forming and accessory minerals Variation in chemical (Borutzky, 1988; Ageeva, 2002; Borutzky, composition and typomorphism 2010; 2012); however some details of this process remain unclear. Two conclusions are The theoretical compositions (wt.%) are as · extremely important. In the first place, two follows: murmanite Na4Ti4Si4O18 4H2O: Na2O types of newly formed minerals are formed: – 16.40, TiO2 – 42.28, SiO2 – 31.79, H2O – · (1) replacement pseudomorphs with relics of 9.53, lomonosovite Na4Ti4Si4O18 2Na3PO4: Na2O primary minerals under conditions of non- – 30.63, TiO2 – 31.59, SiO2 – 23.75, P2O5 – · · equilibrium metasomatic process and (2) pro- 14.03, betalomonosovite Na4Ti4Si4O18 Na2HPO4 ducts of their recrystallization as meta crysts NaH2PO4: Na2O – 22.93, TiO2 – 33.79, SiO2 formed under equilibrium conditions. In the – 25.41, P2O5 – 15.01, H2O – 2.86, or Na4Ti4 · second place, the transformation of primary Si4O18 2NaH2PO4: Na2O – 20.02, TiO2 – rocks of Central Arc of the massif urtite ® 34.64, SiO2 – 26.05, P2O5 – 15.38, H2O – 3.91 feldspar urtite ® juvite ® rischorrite started (ignoring traces). The Si, Ti, P and O contents with fenetization (magmatic replacement) and (O = 26 apfu) in lomonosovite and betalo mo - as temperature and alkalinity of fluid dec- nosovite are identical, whereas Na concentra- reased evolves to lower-temperature acidified tion decreases from lomonosovite to betalo - aqueous solutions; Na minerals are replaced monosovite as consistent with increasing con- by Na,K minerals followed by K minerals to tent of H atoms from 10 Na at 0 H to 7 Na at Na minerals again accompanied with dehy- 3 H apfu (first stage of transformation) to 6 Na dration. at 4 H apfu (second stage). In murmanite with Turning to betalomonosovite, we conclude the same Si and Ti content, P is absent, H and that in addition to its peseudomorphs after O content is 8 and 22 apfu, respectively. Nb, lomonosovite forming at higher temperature Ta, Zr, Fe, Mn, Mg, Ca, K, and F are minor than murmanite under effect of solution en - admixtures in these minerals. riched in K in juvite, rischorrite, and pegma - The first researchers of the lomonosovite tites cutting these rocks, its newly formed more group minerals believed that lomonosovite New data on betalomonosovite 27 and murmanite are the products of magmatic crystallization and continuous solid solution series is between them, although murmanite containing 5.0 wt.% P2O5 was defined by Se - menov et al. (1961) as betamurmanite. After pseudomorphic origin of murmanite being established, the presence of P in it was ex plai - ned by relict lomonosovite. Betalo monosovite is behind this concept and variation in Na and

H2O content in its composition is determined by mineral-forming or mineral-retaining me - dium. We have studied in detail using electron microprobe the chemical composition of accessory lomonosovite and betalomonosovite from the massive coarse-grained and feldspar Fig. 2. Betalomonosovite from arfvedsonite-orthoclase peg- urtite – juvite – pyroxene rischorrite selec - matite vein cutting rischorrite in the Apatite cirque of Mt. Rasvumchorr. Collection of M.N. Sokolova (no. 569). Grain ted from core of holes 1c, 2c, 4c, 1456, and size 3 × 5 mm. 1494 drilled at the Rasvumchorr apatite deposit in Khibiny (Ageeva, 1992, 2002) and The P2O5 content is weakly variable, wt.%: newly for med betalomonosovite from peg- 15.15–11.59 (P 2.14–1.52 apfu; average 1.66 matite ve in hosted in rischorrite from the apfu) in feldspar urtite, 14.80–13.29 (2.07–1.79 Apatite cirque of Mt. Rasvumchorr (specimen apfu; 2.00) in juvite, and 16.95–11.91 (2.29–1.58 of M.N. So kolova) previously examined with apfu; 1.96) in rischorrite. Assuming some un - bulk chemical analysis (Sokolova et al., cer tainty in determination of Na (elimination 19712). The pegmatite sample was used for the under beam) and P (Nb hampers its determi- crystal structure refinement. Electron micro- nation) we state the process differed from su - probe data for lomonosovite and betalomono - pergene mineralization. As is seen from Fig. 3, sovite are given in descending order of Na the lomonosovite and betalomonosovite com- content in Table 1. The formulae are calcula - positions forms two different cluster close to ted on the basis of Si + Al = 4. The Na2O con- theoretical compositions, but tend to the mur- tent (wt.%) in the samples studied is substan- manite composition. However, parts of the tially variable: 29.60–17.63 (Na 9.23–5.42 same grain may correspond to both lomonoso- apfu; average 7.92 apfu) in feldspar urtite, vite and betalomonosovite as illustrated by 9.86–25.94 (9.69–7.99 apfu; 8.85 apfu) in sample 87/1c from rischorrite shown as points juvite, and 28.98–13.57 (9.74–4.21 apfu; 6.96 1 and 2 in Fig. 3 (Table 1, anal. 21, 29). apfu) in rischorrite, i.e., some features of the The elevated Nb2O5 content (wt.%) in compositional distribution of the lomonoso- some samples of both lomonosovite (3.76 – vite group minerals in the rocks of this comp- anal. 3, 5.18 – anal. 6, 9.00 – anal. 20) and be - lex are observed. However, overlapped com- ta lomonosovite (3.82 – anal. 28) with low TiO2 positions in the selected rock groups are es - tablished, for example, from the soda horizon Fig. 3. A Na versus P plot for accessory minerals of the lomo - nosovite group in urtite-juvite-rischorrite complex in the within feldspar urtite (sample 61/2c, anal. 9, Khibiny massif [(Lm) lomonosovite, (b-Lm) betalomonosovite, 38), in rischorrite (sample 50/2c, anal. 22, 35, (Mrm) murmanite. (1) Core and (2) rim of the same grain (sam- 37, 39, 44 and sample 136/2c, anal. 5, 7, 25, ple 87/1c) in rischorrite. 33) and malignite (sample 502/1456, anal. 2, P apfu 19, 36). This testifies to different intensity of lomonosovite alteration, different rate of Na removal and hydration, and not achieved equilibrium during transformation of this rock complex. Accessory minerals with the most stable and closest to lomonosovite composition were observed in juvite, whereas in urtite and rischorrite, both lomonosovite (relict) and betalomonosovite (newly formed) are common, i.e., the formation of betalomonosovite corresponds to the early stage of feldspar al - teration in the rocks of this complex. Na apfu 28 New Data on Minerals. 2014. Vol. 49 Lomonosovite Formula calculated on the basis of Si + Al = 4 apfu 4 = Al + Si of basis the on calculated Formula 2c23.57 1456 21.9227.36 1456 23.08 28.92 23.79 1456 13.05 22.55 23.02 2c 14.25 25.840.95 23.96 12.94 29.87 23.55 14.23 1.890.00 1456 23.42 23.91 13.80 30.18 2c 3.76 0.084.07 23.45 13.88 26.32 23.68 12.98 1.85 – 2.50 27.10 1456 22.82 14.46 27.21 0.54 1.86 23.27 13.66 2c 26.60 0.09 23.38 14.39 5.18 1.97 24.97 24.75 0.06 13.70 1456 24.27 0.00 1.91 23.32 14.34 1c 0.00 26.94 23.94 14.23 1.92 3.34 27.84 23.79 0.39 14.80 1456 25.02 0.00 2.41 24.06 13.81 0.08 25.85 2c 24.79 14.48 0.56 2.55 27.77 23.96 1.71 13.95 25.32 0.76 3.32 24.73 1456 14.20 0.00 20.73 23.96 14.80 0.76 1456 2.79 25.80 0.06 15.15 1456 28.90 1.10 3.24 13.08 – 1456 16.04 0.97 2.79 1c 0.76 0.00 4.44 3.15 0.00 1456 3.09 1494 0.00 0.004.08 3.04 1c 0.63 0.28 4.45 3.64 0.93 0.00 3.52 2.86 2c 9.00 0.00 3.65 2.561.87 0.70 0.06 4.18 2.63 2.19 0.30 0.02 3.75 2.47 1.90 0.00 4.08 2.86 2.020.00 0.06 3.77 2.13 2.02 0.0210.52 3.59 10.30 1.96 0.00 10.07 3.85 1.83 0.00 9.97 3.87 2.04 0.00 9.67 3.75 1.81 0.01 9.76 3.78 2.06 0.05 9.51 3.72 1.97 0.00 9.37 4.10 2.07 0.00 9.55 3.79 2.06 0.00 9.43 3.63 2.02 0.01 9.42 3.84 2.00 0.00 9.29 3.45 2.02 0.00 9.55 3.59 1.99 0.00 9.28 3.54 2.00 0.00 9.21 3.92 2.02 0.00 9.35 2.14 0.00 9.31 1.79 0.03 9.12 2.26 0.00 8.99 0.00 8.80 0.00 8.61 0.01 8.38 80/ 502/ 319/ 275/ 136/ 477/ 136/ 502/ 61/ 309/ 142/ 448/ 80/ 306/ 318/ 306/ 275/ 76/ 502/4.00 101/ 3.980.00 87/ 4.00 0.023.49 50/ 3.98 0.00 3.95 3.99 0.02 2.94 4.00 0.01 3.25 3.92 0.00 3.89 3.98 0.08 2.94 3.68 0.02 3.78 4.00 0.32 3.30 3.88 0.00 3.20 4.00 0.12 3.46 4.00 0.00 3.40 4.00 0.00 3.2326.26 4.00 0.00 3.12 21.43 3.95 0.00 3.27 25.08 25.51 4.00 0.05 3.59 26.33 4.00 0.00 3.10 25.78 25.36 3.99 – 3.27 25.56 3.99 3.47 24.50 0.01 25.76 4.00 3.06 0.00 25.51 3.99 2.60 25.17 – 25.68 3.14 25.18 0.01 3.62 25.87 25.70 25.20 25.40 24.78 25.54 24.12 25.97 102.97 100.65 95.59 99.80 98.91 102.55 100.00 100.07 102.54 99.21 98.07 95.26 98.52 102.16 97.82 102.52 97.27 99.18 99.74 102.01 96.90 99.85 holes in the district of the Rasvumchorr apatite deposit) apatite Rasvumchorr the of district the in holes Chemical composition (wt.%) of accessory lomonosovite and betalomonosovite in the rocks of the urtite-juvite-rischorrite complex (core samples from drill from samples (core complex urtite-juvite-rischorrite the of rocks the in betalomonosovite and lomonosovite accessory of (wt.%) composition Chemical 5 3 3 2 5 O 2 O 30.28 28.13 28.98 29.86 28.09 28.50 28.36 27.94 29.60 27.43 27.10 26.69 26.78 28.25 26.47 27.51 26.96 26.99 27.49 26.31 26.30 24.80 O 2 2 O 2 O 0.00 0.08 0.01 0.00 0.01 0.04 0.25 0.00 0.00 0.00 0.04 0.00 0.00 0.01 0.00 0.01 0.01 0.12 0.00 0.02 0.01 0.07 2 O 2 (Ti+Nb+Fe) (Na+Ca+K) 2 No. anal. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 SiO TiO P Al MnO 0.62 0.57 0.41 0.23 0.22 0.70 0.22 0.57 0.40 0.39 0.28 0.26Mn 0.67Mg 0.50P 0.21 0.09Na 0.68 0.09 0.00Ca 0.00 0.06 0.10 0.49K 0.03 0.06 9.96 0.46 0.03 0.09 9.91 0.56 2.20 0.10 0.02 9.74 0.38 0.92 0.03 0.14 9.69 0.32 0.93 0.08 0.04 9.43 0.28 0.05 0.09 9.23 0.24 0.06 0.00 9.16 0.53 0.04 0.07 9.03 0.29 0.04 0.08 9.01 0.35 0.10 0.02 8.98 0.54 0.07 0.00 8.93 0.45 0.03 0.09 8.90 0.48 0.09 0.03 8.88 0.39 0.00 0.16 8.85 0.67 0.07 0.24 8.80 0.42 0.06 0.04 8.79 0.41 0.31 0.20 8.79 0.56 0.13 0.11 8.70 0.52 0.13 0.09 8.58 0.39 0.11 8.51 0.42 8.25 0.29 8.00 0.36 0.37 Si Al Ti NbFe 0.07 0.16 0.52 0.29 0.34 0.14 0.24 0.04 0.25 0.39 0.25 0.00 0.42 0.14 0.30 0.00 0.32 0.04 0.39 0.06 0.35 0.06 0.41 0.09 0.36 0.07 0.57 0.06 0.38 0.23 0.39 0.00 0.45 0.05 0.36 0.07 0.32 0.68 0.32 0.05 0.31 0.03 0.35 0.27 Table 1. 1. Table sample No. е е O K е Nb Fe MgO – 0.38 0.25 0.38 0.07 0.58 0.15 0.38 0.00 0.27 0.30 0.08 0.00 0.36 0.13 0.66 0.95 0.18 0.83 0.46 0.38 0.43 CaONa 3.07 1.93 1.75 1.55 1.32 2.95 1.58 1.94 3.35 2.49 2.66 2.10 3.65 2.49 2.24 3.15 2.90 2.18 2.43 1.69 2.13 2.01 New data on betalomonosovite 29 2c 1c 1c 1c Betalomonosovite Formula calculated on the basis of Si + Al = 4 apfu 4 = Al + Si of basis the on calculated Formula Lomonosovite 2c26.34 1456 24.2827.26 26.88 2c 26.0414.55 25.00 28.29 13.29 25.81 1c0.76 25.20 14.30 24.43 28.520.09 3.62 14.41 25.22 25.24 2c 11.59 25.723.02 0.77 1.12 26.30 13.38 24.90 25.72 2.70 0.00 13.56 1.43 23.44 1456 27.66 14.20 25.49 1c 2.77 0.04 27.60 0.79 11.69 25.00 28.61 5.09 13.29 0.00 3.82 24.26 24.60 1456 11.91 25.13 2.95 0.11 27.50 0.73 4c 14.11 24.23 27.26 16.50 3.16 0.00 25.21 3.43 28.20 14.57 26.57 1c102.42 2.74 27.32 0.00 1.07 100.04 16.38 25.35 102.52 26.64 99.42 12.34 3.19 24.86 0.00 0.41 15.05 2c 96.97 15.12 26.52 27.50 3.22 0.13 1.26 95.48 13.95 25.41 29.22 1456 94.43 14.36 25.05 4.33 0.00 2.10 20.03 24.86 98.53 2c 13.43 29.60 3.50 0.00 0.50 93.37 15.28 26.60 92.71 16.95 3.84 0.11 0.92 1456 14.02 95.21 2c 2.59 0.06 0.60 94.473.40 95.18 2.64 0.23 0.78 2c 93.32 3.70 2.27 0.01 1.04 93.95 3.56 91.00 2c 3.69 0.00 15.26 94.36 2.071.86 3.74 0.00 2.74 94.03 0.94 1.79 3.66 90.65 0.00 3.11 94.16 12.69 1.80 3.76 0.00 2.87 97.92 0.340.01 1.95 3.52 92.15 0.00 2.82 0.77 90.84 8.39 0.01 1.52 3.62 0.11 2.30 8.44 0.00 0.11 1.84 3.81 1.81 8.09 0.01 1.70 1.82 4.10 8.07 0.01 1.87 3.87 7.74 0.01 1.59 3.58 7.42 0.01 1.91 3.75 7.24 0.01 1.58 3.64 7.28 0.01 1.91 3.78 7.07 0.03 2.29 3.80 7.15 0.01 1.96 3.40 6.92 0.01 2.26 3.24 7.00 0.01 1.66 3.83 0.00 6.58 1.93 3.69 0.01 6.30 1.86 3.54 0.01 6.23 1.96 3.78 3.46 0.03 5.95 1.71 0.17 5.65 2.04 0.00 5.56 2.28 1.90 0.07 5.41 0.37 5.56 0.02 5.44 0.04 4.93 4.77 3.980.02 3.86 0.14 4.00 0.00 3.99 0.01 4.00 0.00 3.98 0.02 4.00 – 4.00 4.00 0.00 3.97 0.00 4.00 0.03 4.00 0.00 3.98 0.00 3.99 0.02 3.96 0.01 4.00 0.04 4.00 0.00 4.00 0.00 4.00 0.00 4.00 – 4.00 – 3.98 3.98 0.00 0.02 0.02 58/ 279/ 136/ 123/ 69/ 142/ 87/ 142/ 307/ 123/ 136/ 142/ 50/ 502/ 50/ 61/ 50/ Pegm. 43/ 17/ Pegm. 50/ 43/ 24.00 24.33 23.72 24.21 23.07 24.14 23.47 23.72 23.36 24.61 23.32 23.72 24.90 23.63 24.48 22.87 22.81 22.69 23.26 22.71 23.83 23.89 23.63 3.10 3.11 3.17 3.03 3.32 3.09 3.14 3.01 3.34 3.52 3.37 2.96 3.39 3.25 3.46 3.26 3.02 1.79 3.33 3.31 2.37 3.54 3.20 Continuation 5 3 3 2 5 O 2 O 27.26 25.94 26.88 24.20 24.40 21.80 22.2 22.28 21.54 19.90 21.34 20.68 19.20 19.06 18.40 17.63 17.82 16.98 16.20 17.17 15.38 14.90 13.57 O 2 2 O 2 O 0.07 0.05 0.01 0.06 0.03 0.04 0.06 0.04 0.03 0.13 0.03 0.05 0.06 0.02 0.07 0.04 0.17 0.86 0.02 0.37 1.85 0.11 0.02 2 O 2 (Ti+Nb+Fe) (Na+Ca+K) 2 SiO Al MnMgP 0.06Na 0.05 0.05Ca 0.09 0.05K 0.02 0.08 7.99 0.05 0.04 7.99 0.39 0.06 0.02 7.76 0.44 0.08 0.13 7.49 0.33 0.08 0.02 7.33 0.57 0.13 0.06 6.88 0.40 0.06 0.05 6.83 0.53 0.00 0.04 6.72 0.40 0.05 0.02 6.71 0.56 0.14 0.19 6.54 0.36 0.12 0.06 6.49 0.58 0.18 0.12 6.42 0.42 0.10 0.06 6.11 0.57 0.11 0.12 5.87 0.46 0.16 0.31 5.82 0.43 0.00 0.07 5.42 0.40 0.03 0.06 5.20 0.52 0.08 0.28 5.19 0.42 0.14 0.01 5.05 0.19 0.07 0.09 5.02 0.36 1.35 4.69 0.47 4.59 0.38 4.21 0.32 0.52 Si Al Notes: Analyses 9, 11, 20, 27, 31, 33, and 38 were obtained on Camebax SX-50 electron microprobe at IGEM RAS, analyst V.V. Khangulov; analyses 1, JSM-5300 35, 37, Link 39, ISIS 40, 44 SEM were at obtained on IGEM RAS, analyst N.V. Trubkin; other (anal. analyses urtite of areas with juvite: 6); were (anal. juvite of areas with 38), obtained 27, 9, (anal. horizons soda with on 23), (anal. urtite fresh of a areas with urtite: feldspar 20); (anal. Cameca horizon) (soda urtite grained MS-46 at IGEM RAS, analyst O.A. Ageeva. Host rocks: subore massive coarse- 4, 14–17, 24), with areas of rischorrite (anal. 10, 12); rischorrite: anal. 3, 5, 7, 13, 21, 22, 25, 28–30, 32–35, 37, 39, 41, 44–45, the same rock with soda horizon: anal. 1, 2, 26; 8, 19, 36, malignite: the same rock anal. with zones of rischorrite: anal. 31; pegmatites in rischorrite and malignite: anal. 11, 40, 42–43. Dash denotes that the data are absent. In number of sample, sam- pling depth over number of drill hole. Table 1. 1. Table sample No. е е е O No. anal.No. 23 24 25 26 27* 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 TiO P Nb Fe MnOMgO 0.46 0.23 0.36 0.40 0.40 0.08 0.58 0.22 0.27 0.26 3.16 0.33 0.97 0.33 0.12 0.58 0.46 0.25 0.32 0.00 0.33 0.22 0.18 0.58 1.37 0.48 0.46 0.78 0.88 0.40 0.48 0.46 0.94 0.73 2.32 – 0.48 0.46 0.13 2.12 0.35 0.90 0.58 0.49 0.38 5.65 Ti NbFe 0.05 0.26 0.34 0.08 0.32 0.10 0.31 0.06 0.61 0.28 0.34 0.05 0.39 0.24 0.33 0.08 0.37 0.03 0.39 0.09 0.55 0.15 0.41 0.04 0.46 0.07 0.32 0.04 0.32 0.06 0.28 0.07 0.44 1.09 0.31 0.15 0.37 0.06 0.35 0.90 0.32 0.02 0.27 0.06 0.22 0.20 K CaONa 2.38 2.59 1.79 3.15 2.36 3.04 2.34 3.25 2.56 3.18 2.52 3.33 2.60 2.42 2.25 3.04 2.59 1.15 2.11 2.88 2.25 2.00 3.05 30 New Data on Minerals. 2014. Vol. 49 content comes to our attention. It is interes - H concentration ranges from 24 to 26 and 1 to ting that Na is partially substituted by K with 2 apfu (exceptional holotype sample from high-level substitution Ti for Nb. For examp - Lovozero), respectively. In general, this sup- le, some betalomonosovites from the Mt. ports that the chemical composition of the

Yukspor pegmatite are K-Nb varieties (Nb2O5 Khibiny lomonosovite is consistent with for- · 12.69 wt.%, Nb 0.90 apfu and K2O 1.85 wt.%, K mula: Na4Ti4Si4O18 2NaH2PO4. 0.37 apfu – anal. 50; Nb2O5 15.26 wt.%, Nb 1.09 apfu and K2O 0.86 wt.%, K 0.17 apfu – Crystal structures of lomonosovite anal. 40). and betalomonosovite: similarity Betalomonosovite from arfvedsonite-feld- and differences spar pegmatite vein (collection of M.N. So ko - lova, sample no. 569) in the Apatite cirque of The crystal structure of lomonosovite was Rasvumchorr was studied in detail. Electron determined by Rastsvetaeva et al. (1971) and microprobe data together with bulk data of was refined by Belov et al. (1977). It was dis- Sokolova et al. (19711) are given in Table 2. As cussed in detail in light of the murmanite these compositions (anal. 1–5) had been nor- structure determined by Khalilov et al. (19651, malized to 16 cations, we recalculated them 19652), Khalilov (1989), and Rastsvetaeva and on the basis of Si + Al = 4. As is seen from Andrianov (1986), general problems of crystal Table 2, the chemical composition of betalo - chemistry and structural topology, and gene - mo nosovite is more or less constant: total tic singularities of murmanite (Belov and Or - alkali constituents is about 6 apfu; amount of ganova, 1962; Belov, 1965; Khalilov and Ma - Ti and isomorphic admixtures is about 4; Si = 4; ka rov, 1966). The crystal structure of betalo- and proportion of P is about 2 apfu, but O and mo nosovite was solved on samples from Lo-

Table 2. Chemical composition (wt.% ) of betalomonosovite from pegmatites of various geological setting No. anal. 123456

SiO2 25.18 25.51 25.05 26.07 25.22 25.27

TiO2 25.01 28.80 28.58 28.77 27.64 30.43

ZrO2 1.89 1.00 0.52 0.71 0.54 –

P2O5 16.12 15.12 14.31 14.55 14.86 14.49 Nb O 1.10 1.70 1.16 1.17 1.01 2 5 }4.78 Ta2O5 – 0.037 0.02 0.012 –

Al2O3 0.69 0.30 0.21 0.30 0.12 0.01

Fe2O3 2.38 3.27 3.37 2.75 3.87 3.04 FeO Bdl – 0.28 – 0.16 – MnO 1.40 0.37 0.03 0.35 0.78 0.48 MgO 0.22 0.20 0.34 0.35 0.22 0.33 CaO 0.62 2.01 2.88 2.68 3.04 3.19

Na2O 17.13 18.28 17.68 17.63 16.19 19.90

K2O 0.88 0.34 0.45 0.40 0.35 0.32 + H2O 3.90 3.83 3.80 4.95 – – }4.60 H2O Bdl Bdl 0.70 Bdl – F–0.59 0.50 0.43 0.64 0.53

O =F2 – 0.25 0.21 0.19 0.27 0.22 Total 100.90 100.54 99.55 100.49 99.67 92.48 Empirical formula calculated on the basis Si + Al = 4 apfu

1. (Na5.11K0.17Ca0.10)е=5.38(Ti2.89Nb0.33Zr0.14Fe0.28Mn0.18Mg0.05)е=3.87(Si3.88Al0.12)е=4P2.10O25.84H4.72

2. (Na5.48K0.07Ca0.33)е=5.88(Ti3.35Nb0.08Zr0.08Fe0.38Mn0.05Mg0.05)е=3.99(Si3.95Al0.05)е=4P1.98O24.74H2.01F0.29

3. (Na5.42K0.09Ca0.49)е=6.00(Ti3.40Nb0.12Zr0.04Fe0.45Mn0.00Mg0.07)е=4.08(Si3.96Al0.04)е=4P1.92O24.83H1.83F0.25

4. (Na5.17K0.08Ca0.45)е=5.70(Ti3.28Nb0.08Zr0.05Fe0.31Mn0.05Mg0.08)е=3.85(Si3.95All0.05)е=4P1.86O23.59H1.19F0.21

5. (Na4.95K0.07Ca0.51)е=5.53(Ti3.28Nb0.08Zr0.04Fe0.48Mn0.10Mg0.05)е=4.03(Si3.98Al0.02)е=4P1.98O24.31H1.24F0.32

6. (Na4.26K0.06Ca0.54)е=4.86(Ti3.62Nb0.07Fe0.36Mn0.06Mg0.08)е=4.19(Si4.00Al0.00)е=4P1.94O23.77F0.27 Notes: (1) Lovozero massif, Tulbn'yunuai river, pegmatite hosted in nepheline-sodalite poikilitic syenite, analyst M.E. Kazakova (Gerasimovsky and Kazakova, 1962); (2–6) Khibiny massif, Apatite cirque of the Rasvumchorr deposit: (2) rischorrite, (3–5) arfvedsonite-feldspar pegmatite veins cutting rischorrite, analyst N.I. Zabavnikova (Sokolova et al., 19712), (6) the same, sample no. 569, collection of M.N. Sokolova, structurally refined in this study, electron-microprobe analysis. Total of anal. 3 includes 0.024 wt.% SrO; total of anal. 5 includes, wt.%: 0.018 Li2O, 0.013 Rb2O, 0.0007 Cs2O, 0.007% SrO, analyst G.Ye. Kalenchuk. No water was analyzed in anal. 6. New data on betalomonosovite 31

vo zero by Khalilov and Makarov (1966), Kha - 3+ (Na4.42Mn0.11Ca0.71K0.07)е5.31(Ti3.63Nb0.03Fe 0.34)е4.00 lilov (1990), and Rastsvetaeva (1986, 1988, O2[(O,OH)0.79F0.21]2[Si2O7]2[H2PO4]2. The unit 1989) as well as sample from Khibiny (Rasts- cell dimensions are a = 5.3184(3), b = vetaeva et al., 1975). 7.0869(5), c = 14.4490(10)Å, a = 102.944(7)°, As the data on the discussed structures b = 96.367(7)°, g = 90.331(6)°, V = 527.22(6)Å3, were obtained long enough and some new 3 Dcalc. = 2.91 g/cm . Space group is P1. members of the lomonosovite group were dis- The comparison of the structures indi- covered to date, these structures should be cates. refined with the state methods and revision of Lomonosovite is disilicate. According to crystal chemical features. Cámara et al. (2008) Cámara et al. (2008), its structure is based on performed this study for the lomonosovite and the TS titanosilicate blocks with formula murmanite structures, but the structure of P H O A 2M 2M 4 (Si2O7)2X4, alternated along axis c betalomonosovite attributed to discredited with intermediate blocks I corresponding in minerals was not refined. Yakubovich et al. composition to Na6(PO4)2 (Fig. 4a). The TS (2014) refined it and below it is compared with block consists of octahedral layer O com- the structure of lomonosovite. posed of close packed octahedra MO(2) – Unfortunately, the sample refined by Cá- [6]TiO(2) and [6]NaO(2) as brookite-type chains mara et al. (2008) cannot be regarded as ty - 8– (Ti2O8) linked with Na octahedra in similar pical lomonosovite, because it was selected configuration in ratio Ti:Na = 1:1 (Na2Ti2 per from fine fraction of the Lovozero bornema- cell) (Fig. 5a), and heteropolyhedral layer H nite that is secondary mineral replacing lomo- composed of MH polyhedra – [6]TiH(1) octa - nosovite, i.e., it is originated from different hed ra bonded with Si2O7 groups and eight- geological environment than the Khibiny lo - fold polyhedra [8]NaH(1) (Fig. 5b). Connecting monosovite genetically related to the dis- P layer is conditionally determined because cussed betalomonosovite. However, our exa - two Si2O7 groups are linked with the nearest mination of this uncommon and deficient [6]TiO(2) octahedra of the brookite chains via material showed the power of modern struc- oxygen atoms (Fig. 5c) while [6]TiH(1) octahe- tural methods and allowed justification of si - O dron shares apex occupied by oxygen X M = tes, their occupancies by trace elements, and O(8) with two [6]NaO(2) and one [6]TiO(2) (octa- determination of iron valence with the Möss - hedra of the O layer (Figs. 5b, 5с). Tetra hed - bauer method. By the way, the Fe2+/Fe3+ = rally coordinated P bonded with Na polyhedra 58/42 value of 58/42 indicates long transition of three types [6]Na(3), [4]Na(4) and [5]Na(5) from reductive to oxidative formation condi- occurs in block I (Fig. 4a). tions, whereas the Lovozero murmanite was As aforementioned, the ideal structural formed under oxidative conditions (iron is formula of lomonosovite regardless isomor- completely trivalent). phic admixtures is Na10Ti4(Si2O7)2(PO4)2O4 The empirical formula of lomonosovite (Z = 1). The both Ti sites contain Nb, Fe, Mn, [6] H with refined structure (Na9.50Mn0.16Ca0.11)е9.77 and Mg admixtures, but Ti (1) octahedron is 2+ 3+ (Ti2.83Nb0.51Mn0.27Zr0.11Mg0.11Fe0.10Fe0.06Ta0.01)е4.00 dominated by Ti. Small portion of vacancy

(Si2.02O7)2(P0.98O4)2(O3.50F0.50)е2, calculated on o0.05 per cell occurs in eight-fold polyhedron the basis of 26 (O + F) anions from the com- [8]NaH(1) and octahedron [6]NaO(2); octahedron position determined on a Cameca SX100 elec- [6]Na(3) of the I layer contains 0.11 apfu Ca, tron microprobe is consistent with the struc- and tetrahedron [4]Na(4) contains 1.71 Na + 2+ tural formula Na10Ti4(Si2O7)2(PO4)2O4 (Z = 1). 0.16 Mn + 0.13 o. The calculated valence O The unit cell dimensions are a = 5.4170(7), force at site X A = O(9) bonded with two b = 7.1190(9), c = 14.487(2)Å, a = 99.957(3)°, atoms Ti(2) and atom Na(2) in the O layer and b = 96.711(3)°, g = 90.360(3)°, V = 546.28(4)Å3, atom Na(1) in the H layer is lesser than that at 3 O Dcalc. = 3.175 g/cm . Space group is P1 (Cáma - site X M, occupied only by O atoms and linked ra et al., 2008). with Ti(1) in the H layer and Ti(2) and two We refined the crystal structure of the Na(2) in the O layer (Fig. 5с) (1.84 against Khibiny betalomonosovite on the material 2.05 v.u.) that is consistent with the partial from pegmatite in the Apatite cirque of Mt. substitution of F for O according to the reac- Rasvumchorr. The chemical composition de - tion: Ti4+ + O(9)2– ® M2+ + F– with the sub- ter mined on a JEOL JXA-8200 electron micro- stitution of Ti at site TiO(2) with divalent ele- 2+ probe (Table 2) are normalized on the basis of ments Mn0.22Mg0.11Fe 0.05 (0.38 apfu).

4 (Si + Al) atoms to formula (Na4.26Ca0.54 K0.07)е4.87 The refined crystal structure of beta lo -

(Ti3.66Nb0.07Fe0.36Mn0.07Mg0.08)е4.24Si4P1.96O23.54F0.27, monosovite (Yakubovich et al., 2014) is distin- corresponding to the crystal chemical formula guished by some features (Table 3). In the O 32 New Data on Minerals. 2014. Vol. 49 layers of the TS blocks, Ti sites M2[6] corre- is always Ti dominated. The elevated content sponding to MO(1) = [6]TiO(2) in lomonosovite of trace elements is observed at Na sites lin- (Fig. 4b) are also completely occupied, but ked with Ti; in this case, NaO(2) contains not with Fe admixture only, whereas all-Na octa- only Ca, but Mn, and in eight-fold NaP(1) po - hedra MO(2) = [6]Na(2) of lomonosovite are lyhedra, where Cámara et al. (2008) found K in transformed to seven-fold polyhedra M5[7] in murmanite, Mn could be incorporated into betalomonosovite and are half occupied by the structures of the Khibiny lomonosovite Na with Ca admixture, whereas another half is and betalomonosovite, where elevated K and vacant (Fig. 5d). In the H layers of the TS Nb contents were found (Table 1). Few vacan- blocks the Ti dominated M1[6] octahedra cor- cies are typical of these Na sites in lomonoso- responding to octahedra MH = [6]TiH(1) in lo - vite and betalomonosovite. However, their monosovite are also completely occupied, but amount is disparate with vacancies in the only with Ti and Nb; Ca incorporates into all- structure of betalomonosovite from Rasvum - Na eight-fold polyhedra AP = [8]Na(1) depic - chorr that is the most important feature of the ted as M4[8], and nearly half polyhedra is mineral studied here. vacant (Fig. 5e). The differences in the structure of the Therefore, Ti content in the TS blocks of intermediate I block in the structure of beta - betalomonosovite is elevated; Na is partly lomonosovite as compared with lomonosovite substituted by Ca; and nearly half Na is remo- highlight this feature (Table 3). All-Na five- ved. However, the crystal chemical analysis fold polyhedron [5]Na(5) in lomonosovite cor- should be careful because isomorphic admix- responds to M3[6] octahedron less than half tures in the minerals from different geological occupied and contaminated by Mn (0.762 Na environment are compared. The additional + 0.118 Mn + 1.12 o) in betalomonosovite. com parison with the structure of murmanite Tetrahedron [4]Na(4) (1.71 Na + 0.16 Mn + from Lovozero (Cámara et al., 2008) shows that 0.13 o) with simi lar occupancy and small the greatest occupancy of TiO(2) octahedral in vacancy was such polyhedron in lomonoso- brookite chains with various isomorphic ad - vite. The [4]Na2, polyhedron occupied with Na mix tures is common in the discussed minerals only for eight (0.24 Na + 1.76 o) corresponds of the lomonosovite group, whereas octahe- to it in betalomonosovite. Eight-fold [8]Na1 po - H lyhedron that was octahedron and contained dron Ti (1), linked with disilicate groups Si2O7 a b [Si2O7] [6]M1 =Ti/Nb O [6] H [8] H H = [Si2O7], Ti , Na [8]M4 =Na/Ca + o MO = [6]NaO, [6]TiO O [6] H [8] H H = [Si2O7], Ti , Na

MP = [6]NaP, [5]NaP, [4]NaP ® TS block [6]M2 =Ti/Fe MH MO [Si O ]X [7]M5 =Na/Ca + o

2 ® 4 2 7 4

I block [6] Na6(PO4)2 M3 =Na/Mn + o [4]Na2 + o [4]P(1,2) ® c TS block c [8]Na1

® [8]M4 =Na/Ca + o

b b

Fig. 4. Comparison of crystal structures of lomonosovite (Cámara et al., 2008), and betalomonosovite (Yakubovich et al., 2014):

(a) structure of lomonosovite projected onto (100), titanosilicate (TS), heteropolyhedral (I), and Na-P Na6(PO4)2 blocks alternated along axis c; (b) structure of betalomonosovite, view along diagonal of the ab face, alternation of the same blocks along axis c; the unit cells are shown as rectangles; disilicate groups Si2O7 are red-orange; Ti-octahedra are blue; differently coordinated Na polyhedral are green; P tetrahedral are yellow; and oxygen atoms are red circles. New data on betalomonosovite 33

a d

b e

c f

Fig. 5. Comparison of crystal structures of lomonosovite (a–c) (Cámara et al., 2008) and betalomonosovite (d-f) (Yakubovich et al., 2014) projected perpendicular to axis [001]: (a) close packed Ti and Na octahedra of octahedral O layer from TS block in lomonosovite;

(b) disilicate groups Si2O7, Ti octahedral, and Na eight-fold polyhedral of heterepolyhedral H layer from TS block; P O O (c) junction of octahedral and heteropolyhedral layers in TS block, main oxygen atoms in Ti and Na polyhedra X M, X M and X A (see text) are shown; (d) probable distribution of vacancies in Na polyhedra of octahedral O layer from the TS block in betalomonosovite; (e) titanosilicate "maille" of heteropolyhedral H layer from the TS block with Na eight-fold polyhedra in cavities; 2+ (f) defect Na-P layer {Na3.00Mn0.11[H2PO4]2} in betalomonosovite with oxocomplexes [(P2O4)0.5O2] composed of two phosphate tetrahedra with different filling put into each other.

Ca ([6]Na(3) = 1.89 Na + 0.11 Ca) in lomo- cantly rearranged and degree of their occu- nosovite becomes all-Na. In other words, Na pancy substantially decreases (proportion of polyhedra are substantially reorganized: tet - vacancy increases = 2.88 o). ra hedra are retained (Na(4) ® Na2), whereas The split of P site is also substantial that lomonosovite five-fold Na(5) polyhedron and was previously reported by Rastsvetaeva et al. octahedron Na(3) are modified to octahedron (1975). According to their data, position of P2 M3 and Na1 eight-fold polyhedron, respec- corresponded to that in lomonosovite, where- tively (Fig. 5f). According to Rastsvetaeva et as the second P1 was turned around that al. (1975), two couples of Na6 and Na7 eight- resulted in the P–O chain. Our version of the fold polyhedra and nonpaired octahedron Na5 structure shows that phosphorus site is split to disturbing centrosymmetric structure occur in P1 and P2 at inadmissible short distance of this block. Thus, in I block of betalomonoso- 0.53Å, and therefore there is a 50% chance that vite, Na polyhedra (determined by various these positions will be occupied, as well as, investigators in different ways) are signifi- two of four apices occupied by oxygen atoms 34 New Data on Minerals. 2014. Vol. 49

Table 3. Comparison of cation sites in the crystal structures of lomonosovite (Cámara et al., 2008) and betalomonosovite (our data) as indicated by various authors and their occupancy Lomonosovite Betalomonosovite (Cámara et al., 2008) (Yakubovich et al., 2014) MO(1)=[6]TiO(2) 1.31 Ti+0.22 Mn2++0.20 Nb+0.11 Zr+0.05 Fe2++0.11 Mg=2.00 M2[6] 1.66 Ti+0.34 Fe=2.00 MO(2)=[6]NaO(2) 1.95 Na+0.05 o=2.00 M5[7] 0.63 Na+0.37 Ca+1.00 o=2.00 MH=[6]TiH(1) 1.52 Ti+0.05 Mn2++0.31 Nb+0.01 Ta+0.06 Fe3++0.05 Fe2+=2.00 M1[6] 1.97 Ti+0.03 Nb=2.00 AP=[8]Na(1) 1.95 Na+0.05 o=2.00 M4[8] 0.78 Na+0.34 Ca+0.88 o =2.00 [4]P 2.00 P P1[4] 1.00 P P2[4] 1.00 P [5]Na(5) 2.00 Na M3[6] 0.76 Na+0.12 Mn+1.12 o=2.00 [6]Na(3) 1.89 Na+0.11 Ca=2.00 Na1[8] 2.00 Na [4]Na(4) 1.71 Na+0.16 Mn2++0.13 o=2.00 Na2[4] 0.24 Na+1.76 o=2.00 Notes: The site occupancy in betalomonosovite is shown for complete cell to compare with lomonosovite, i.e. it is duplicated; in this case, vacancies in its structure are better displayed.

O12 and O12A, and O13 and O13A in phos- Na3PO4 to complete loose of Na-phosphate phate tetrahedra input into each other that constituent. The degree of replacement of leads to the formation of orthocomplexes lomonosovite by murmanite depended on the

[(P2O4)0.5O2] in average structure (Fig. 5f). The degree of bucking and time of water treat- deficient valence force and overestimated ment. The scheme proposed by I.D. Borne- O–P distance for these oxygen atoms man-Starynkevich and N.I. Zabavnikova is (0.66–1.00 v.u. and 1.513–1.547Å) relative to used in literature to explain pseudomorphic other atoms O11 and O4 in P tetrahedral (1.61 nature of murmanite. and 1.96 v.u. and 1.497–1.508Å, respectively) Recently, Selivanova et al. (2008) and Se li - suggest that they are transformed to OH vanova (2102) performed experiments on lo - groups and are donors of hydrogen bonds monosovite hydrolysis and cation ex change, linking orthocomplexes and Na polyhedra. but worse carefully (the samples were soaked Thus, betalomonosovite substantially dif- only 0.5–48 hours at room temperature or fers from both lomonosovite and murmanite in 1–100 hours at 74–80°С). It is surprisingly the arrangement of H atoms in the structure. that any result has been obtained, especially According to (Cámara et al., 2008) in murman- when the dependence of dehydration degree ite, blocks TS are linked through outer anions on the trace element content in the structure P H X M of titanium M = Ti(1) octahedra and of lomonosovite has been established. Ne - P P anions X A of sodium A = Na(1) eight-fold vertheless, Selivanova's objection of classic polyhedral, in which oxygen atoms O(10) and concept of pseudomorphic nature of murma ni-

O(11) are substituted by H2O groups and te as a supergene alteration product of lomo - donor-acceptor hydrogen bond arises bet - nosovite caused a discussion in literature. ween oxygen atoms of different oppositely Lykova et al. (2012) repeated runs in distil- oriented H2O groups or with non-substituted lated water at room temperature for 1000 ho urs oxygen atoms O(2)a and O(4)a. Hydroxyl for lomonosovite and betalomonosovite samp - groups are absent in the structure of murma - les of 75 mg in weight crushed to 0.5–1.5 mm nite. in size. These experiments showed that alteration is very slow in distillated water at room Hydration of lomonosovite temperature and geological time is required and water in the structure. to obtain the expected result. The rate of Na Thermal analysis and P leaching from the intermediate layer in the structure of lomonosovite increases at The hypothesis of the secondary origin of 90°С: Na and P contents decrease from 9.5 to murmanite, its formation as a result of Na 5.4–3.0 apfu and from 2.0 to 0.7–0.6 apfu, leaching and hydration, was proposed for the respectively, i.e., the rate of Na removal is first time by Borneman-Starynkevich (1946) much higher than that P with d001 changing and experimentally confirmed by Zabav ni - from 14.2 to 12.7Å in final phase. kova (1967); in the course of experiments, It is important that in the first place, the milled lomonosovite was treated by water at rate of Na and P leaching from betalomonoso- room temperature during one year; Na and P vite is half of that from lomonosovite: only released from mineral as Na orthophosphate 0.4% P2O5 and 0.5% Na2O were leached from New data on betalomonosovite 35 fraction -0.25 to +0.1 mm during 6 months at the bend at 271°C and minimums at 382 and room temperature, whereas from lomonoso- 406°C followed by clear exothermic effect at vite 2.0 and 3.3%, respectively, i.e., betalo - 625°C corresponding to rebuilding of the min- monosovite is more persistent to affecting eral structure and two symmetric endothermic neutral solutions than hyperagpaitic lomo- effects with maximum at 761 and 852°C not nosovite. In the second place, Na is leached accompanied with weight loss and correspon- only from the Na-P intermediate layer of the ding to two stage of the minerals melting. The lomonosovite structure at room temperature, DTG curve shows that most weight (11.01 wt.%) but it does not remove from titanosilicate is lost during three stages (1.86, 3.65, and layer as established by Selivanova et al. 5.50 wt.%) within the range 235–720°C. As is (2008). The data of Lykova et al. (2012) sup- seen from the TG curve, at high temperature port the classic conclusion that murmanitiza- the weight is lost evenly and is not related to tion of lomonosovite is resulted from the the high-temperature endothermic peaks on effect of neutral of weakly acidic low-tempe - the DSC curve. rature solutions although a long time is requi - The thermogram of murmanite (Fig. 6c) red. More stable linkage of Na-P clusters in recorded for the sample of 190 mg in weight betalomonosovite than that in lomonosovite differs enormously from that of lomonosovite was explained by hydrogen bonds, which are and betalomonosovite in both shape and typical of acidic salts Na2HPO4 or NaH2PO4 weight loss (27.16 wt.%). The DSC curve of (Sokolova et al., 19712; Rastsvetaeva et al., mur manite exhibits strong symmetric endo - 1975). In contrast to murmanitization, lomo - thermic effect at 275°C corresponding to a nosovite is replaced by betalomonosovite at weight loss of 17.88 wt.% related to water re - higher temperature in strongly alkaline medi- moval from the mineral. This effect is followed um with substantial Na removal. Our data by a pronounced curve bend at 450°C corre- indicate that Na is leached from both interme- sponding to the major stage of weight loss. diate I layer and titanosilicate TS layer. The clear symmetric endothermic peak at We obtained the new data on thermal be - 726°C corresponds to the mineral melting havior of the lomonosovite group minerals. accompanied with loss of residual water Thermograms were obtained on a Q-1500D de - (1.94 wt.%) that is exhibited as small peak at rivatograph, Hungary equipped with an Eco - 733°C on the DTG curve. This peak is followed khrom complex for the data recording and pro- by a clear bend at 993°C on the DSC caused by cessing within the range from 25 to 1000°С. energy consumption for the structure rebuil- The samples were placed into platinum cru- ding in the murmanite melt. The analysis of cibles and heated in air with rate of 15 deg - the DTG curve reveals two types of water in ree/min; the Al2O3 sample of 200 mg in weight the structure of murmanite: weakly bound was used as reference material. (17.88 wt.%) quickly removed in the narrow The lomonosovite thermogram (Fig. 6a) was temperature range up to 275°C with maximum recorded for the sample of 228 mg in weight. at 177°C and tightly bound (7.34 wt.%) gradu- The DSC curve of lomonosovite exhibits one ally released up to the mineral melting. pronounced high-temperature endothermic Thus, the minerals studied here are dra- peak at 871°C corresponding to the melting of matically different in thermal curves. Total mineral and two weak endothermic effects at weight loss with heating increases from lomo- 941 and 992°C not accompanied with weight nosovite through betalomonosovite to mur- loss and reflecting energy input for the pro- manite (2.65, 14.10, and 27.16 wt.%, respec- cesses in the lomonosovite melt. This energy tively). However, the review of thermograms was probably to be consumed for rebuilding of does not allow consideration of betalo mono- crystalline clusters composed of the SiO4 and sovite as an intermediate product of transfor- РО4 tetrahedra. In the low-temperature region mation of lomonosovite to murmanite with Na of the curve, two insignificant bends are ex - leaching and hydration. In the first place, it is hibited at 248 and 250°C accompanied with indicated by the exothermic effect on the DSC insignificant weight loss of 0.68 and 0.48 wt.%. curve of betalomonosovite corresponding to They are evidently caused by the evaporation the rebuilding of the mineral structure accom- of water and NaF. panied with the substantial energy release. If The thermogram of betalomonosovite re - betalomonosovite was intermediate member corded for the sample of 227 mg in weight dif- of the lomonosovite-murmanite series then we fers fundamentally from that of lomonosovite could observe comparable or more prono un - (Fig. 6b). The DSC curve exhibits triple endo - ced energy outbreak related to the end mem - thermic effect in the range of 237 to 550° with ber recrystallization. However, it was obser - 36 New Data on Minerals. 2014. Vol. 49 ved neither in our experiments nor on the pre- It does not matter if betalomonosovite is viously published DCS curves of lomonoso- approved by the Commission as individual vite and murmanite. In general, our results mineral species or variety of lomonosovite. It supplement the data of previous investigators, is necessary that this term should not be lost who terminated sample heating before mine - with nomenclature changes. However, we ral mel ting. think that betalomonosovite has more reasons to be approved as mineral species than many Status of betalomonosovite "new minerals" recently approved by the Commission using only recommended formal The history of the betalomonosovite dis- chemical and crystal chemical criteria regard- creditation is tortuous. Having acted on be - less genesis, i.e., analysis of formation condi- half of the Commission on New Minerals and tions, stability field of a described mineral, Mineral Names of International Mineralogical and its importance for geo logy. Association formed in 1959 with the revision Unfortunately, well-known story of data of minerals discovered in 1959–1960 and not generalization and formalization in determina- approved by the Commission Villarroel and tion of mineral species was about lomo no sovite Joel (1967) were quite delicate in this ques- and betalomonosovite, as a result of which mi- tion. They evidently understood the impor- neral is separated away from the parent geo- tance of the terms b lomonosovite and meta- logical system and is transformed from the real murmanite and remained them with a signifi- chemical compound to abstract di vorced from cance of 60% or higher; however, they disc - formation conditions and field of stability within redited notions metalomonosovite (= b lo - which its chemical composition, structure, and mo nosovite) and ortholomonosovite (= lomo- physical properties evolve during geological nosovite). In the similar publication, Nickel time in accordance with the evolution of and Mandarino (1988) put dogmatically beta - physicochemical parameters of mineral-for - lomonosovite into the list of already discredit- ming and mineral-retaining medium. ed mineral name that is surprisingly because, in the first place, this mineral was studied in Conclusions detail meanwhile and this term was used in literature concerned with mineralogy of alkaline The novel data obtained and detailed re- complexes; in the second place, its discredita- view of this problem support necessary reha- tion was argued by the references to the afore- bilitation of indefinitely discredited term be - mentioned article published in 1967, in which, ta lomonosovite. This mineral substantially as we know, discreditation was not discussed. differs in the chemical composition, structural

6a MG ТГ 1.55 mg 0.68% 228 1.08 mg 0.48% 238 1.90 mg 0.83% 365 224 1.57 mg 0.66% 779 TIME 0 10 20 30 40 50 мВ ДТА -20 -80 248 -140 240 993 942 -200

-260 -320 871 TIME 0 10 20 30 40 50 мВ 6 4 2 0 365 779 -2 ДТГ -4 871 -6 238 334 -8 TIME 0 10 20 30 40 50 New data on betalomonosovite 37

6b MG 13.52 mg ТГ 1.46% 226 4.24 mg 1.86% 237

335 8.28 mg 214 3.65%

391 12.49 mg 5.50% 202 3.69 mg 1.63% 720 TIME 0 10 20 30 40 50 мВ ДТА

-20

-50 623 1001 -80

-110 271

-140 751 597 852 TIME -170 382 406 0 10 20 30 40 50 мВ 0 237 ДТГ 720 -6 76 -12

-18 335 -24 391 -30 -36 403 371 TIME 0 10 20 30 40 50

MG ТГ 6с 190 33.98 mg 13.95 mg 17.88% 7.34% 175

160 11.65 mg 6.13% 2.30 mg 275 1.21% 3.69 mg 145 1.94% 473 660 TIME 0 10 20 30 40 50 мВ ДТА

-50

-110

-170 189 993 -230 726 TIME 0 10 20 30 40 50 мВ ДТГ 660 473 733 -10 275 298 -40

-70

177 -100 TIME 0 10 20 30 40 50

Fig. 6. Thermograms of the lomonosovite group minerals, our data: (a) lomonosovite (weight 228 mg, weight loss 6.04 mg, 2.65%); (b) betalomonosovite (weight 227 mg, weight loss 32.04 mg, 14.10%); (c) murmanite (weight 190 mg, weight loss 57.62 mg, 27.16%).

A Q-1500D derivatograph (МОМ, Hungary), 25–1000°С, platinum crucibles, heating rate 15 degree/min, 200 mg Al2O3, as reference sample; measurement at air. Analyst P.M. Kartashov. 38 New Data on Minerals. 2014. Vol. 49 singularities, and physical properties from in terms of the crystal structure of lomo- both lomonosovite, with which the rese archers nosovite // Geokhimiya. 1962. No. 1. who do not know enough with nuan ces of min- P. 6–14 (in Russian). eralogy of alkaline complexes formally attempt Borneman-Starynkevich I.D. On the chemical to associate it in the recent mine ralogical no- na ture of murmanite // Problems of Mine ra lo- menclature, and murmanite with which it is fre- gy, Geo chemistry, and Petro graphy, Moscow: quently associated in the lomonosovite-mur - AN SSSR. 1946. P. 66–74 (in Russian). manite solid solution, whe re be talomo nosovite Borutzky B.Ye. Rock-forming mineral of peral- is not end-member. It is really genetically rela - kaline complexes. Moscow: Nauka. 1988. ted to lomonosovite, but is a product of meta- 212 p. (in Russian). somatic alteration of lomo nosovite, recrystal- Borutzky B.Ye. Recent concept of nature and lization and crystallization at high-temperature geological history of rocks of the Khibiny fenitization of rocks of alkaline magmatic com- massif (Critical comparison of proposed plexes with variable basicity of mineral-for - hy po theses and comments) // Unique Ob - ming fluids rather than supergene alteration jects of the Kola Peninsula: Khibiny. Proc. like murmanite. In other words, this mineral All-Russia Conf. 80 Anniv. Kola Sci. Cen - could be defined reasonably as individual ter Russian Academy of Sciences, Apatity. mineral spe cies characterized by discrete che- 2010. P. 7–30 (in Russian). mical composition and structural singularities, Borutzky B.Ye. The essays on fundamental with certain field of stability and studied com - genetic mineralogy: 6. Experience of using positio nal variations resulted from variable detail mineralogical investigation to resol - character of mineral-forming and mineral- ve problems of rock and ore formation: retaining medium. case of study Khibiny massif // New Data on Minerals. 2012. Vol. 47. P. 128–157. Acknowledgments Bussen I.V., Sakharov A.S. Petrology of the Lo- vozero Alkaline Massif. Leningrad: Nau ka. We thank M.N. Sokolova for permanent 1972. 296 p. (in Russian). interest in our study and samples of previous- Cámara F., Sokolova E., Hawthorne F.C., Abdu Y. ly studied betalomonosovite from the Ras - From structure topology to chemical com- vumchorr pegmatite kindly placed in our dis- position. IX. Titanium silicates: revision of posal for structure investigation. the crystal chemistry of lomonosovite and murmanite, Group IV minerals // Miner. References Mag. 2008. V. 72. № 6. P. 1207–1228. Dorfman M.D. Mineralogy of Pegmatites and Ageeva O.A. Typomorphism of accessory lo- Weathering Profiles in Ijolite-Urtite of Mt. monosovite from the rocks of the Khibiny Yukspor, Khibiny Massif. Moscow-Lenin- massif // Zap. Ross. Mineral. O-va. 1999. grad: AN SSSR. 1962. 168 p. (in Russian). Vol. 128. No. 2. P. 99–104 (in Russian). Dudkin O.B. Structural features of giant peg- Ageeva O.A. Typomorphism of Accessory Mi - matite body in ijolite-urtite of Mt. Yuk - nerals and Evolution of Mineral Formation in spor, Khibiny // Proc. Mineralogy of the the Rocks of Rischorrite Complex, Khi biny Kola Peninsula. Kirovsk: Kola Branch AN Massif // Diss. Cand. Geol.-Min. Sci. Mos - SSSR. 1959. No. 1. P. 14–19 (in Russian). cow: IGEM RAS. 2002. 180 p. (in Rus sian). Dudkin O.B. Kozyreva L.V., Pomerantse va N.G. Ageeva O.A., Borutzky B.Ye. To typomorphism Mineralogy of Apatite Deposits of the Khi - of the lomonosovite group minerals // biny Tundra Moscow-Leningrad: Nau ka. Mineralogy at the Turn of XIX Century. 1964. 236 p. (in Russian). Abstract. vol. Moscow: VIMS. 1997. P. 4 (in Es'kova E.M. On the lomonosovite-murmanite Russian). group minerals // Tr. IMGRE AN SSSR. Belov N.V. Essays of structural mineralogy. 1959. No. 2. P. 110–123 (in Russian). XVI. Murmanite // Mineral. Proc. Lvov Gerasimovsky V.I. Lomonosovite, a new mi - Geol. Soc. 1965. Vol. 19. No. 3. P. 295–305 neral // Dokl. AN SSSR. 1950. Vol. 70. (in Russian). No. 1. P. 83–86 (in Russian). Belov N.V., Gavrilova G.S., Solov'eva L.P., Gerasimovsky V.I., Kozakova M.E. Betalo mo - Khalilov A.D. The refined structure of nosovite // Dokl. AN SSSR. 1962. Vol. 142. lomonosovite // Dokl. AN SSSR. 1977. No. 3. P. 670–673 (in Russian). Vol. 235. No. 5. P. 1064–1067 (in Russian). Gutkova N.N. Murmanite, a new titanosilicate Belov N.V., Organova N.I. Crystal chemistry from the Lovozero tundra // Dokl. AN SSSR, and mineralogy of the lomonosovite group ser. A. 1930. No. 27. P. 731–736 (in Russian). New data on betalomonosovite 39

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