Записки горного института, 2023, № 4

          The scientific periodical “Journal of Mining Institute” is published since 1907 by Saint Petersburg Mining University - the first higher technical educational institution in Russia, founded in 1773 by the decree of Catherine II as the embodiment of the ideas of Peter I and M.V. Lomonosov on the training of engineers for the development of mining business.

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              The cover shows an exhibit of the Mining Museum - apatite - green-blue prismatic translucent crystals in yellow-pink calcite with phlogopite (Slyudyanskoye deposit, Mamsko-Chuisky district, Irkutsk region, Russia). The sample was received in 1974 as one of the gifts for the 200th anniversary of the LMI. Apatite is a raw material for the production of phosphate fertilizers, phosphorus and phosphoric acid; it is used in ferrous and non-ferrous metallurgy, in the production of ceramics and glass. The mineral is rarely used by jewelers because of its low hardness and brittleness

              The Mining Museum is the world’s third largest natural-science exposition, it contains more than 230 thousand exhibits, including precious metals and stones, unique collections of minerals, ores, rocks, paleontological remains, meteorites, a collection of models and prototypes of mining equipment, pieces of stone-cutting and jewelry art.

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  JOURNAL OF MINING INSTITUTE
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Volume 262

ST. PETERSBURG • 2023

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University, Saint Petersburg, Russia)
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A.E.Cherepovitsyn, Doctor of Economics, Professor, Head of Department of Economics, Organization and Management (Saint Petersburg Mining University, Saint Petersburg, Russia)
Ya.E.Shklyarskiy, Doctor of Engineering Sciences, Professor, Head of the Department of General Electric Engineering (Saint Petersburg Mining University, Saint Petersburg, Russia)
VAShpenst, Doctor of Engineering Sciences, Professor, Dean of Energy Faculty (Saint Petersburg Mining University, Saint Petersburg, Russia)
Oleg Antzutkin, Professor (University of Technology, Luleo, Sweden)
Gabriel Weiss, Doctor of Sciences, Professor, Pro-Rector for Science and Research (Technical University, Kosice, Slovakia)
Hal Gurgenci, Professor (School of Mining Machine-Building in University of Queensland, Brisbane, Australia)
Edwin Kroke, Doctor of Sciences, Professor (Institute of Inorganic Chemistry in Freiberg Mining Academy, Freiberg, Germany)
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Sections
• Geology • Geotechnical Engineering and Engineering Geology • Economic Geology • Energy




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E S? Э Journal of Mining Institute. 2023. Vol. 262
       Contents

CONTENTS



Geology

     Viktor I. Alekseev. Wodginite as an indicator mineral of tantalum-bearing pegmatites and granites ..................................................................................... 495

     Laysan I. Salimgaraeva, Alexei V. Berezin. Garnetites from Marun-Keu eclogite complex (Polar
Urals): geochemistry and the problem of genesis .............................................. 509

     Anastasia V. Sergeeva, Alexey V. Kiryukhin, Olga O. Usacheva, Tatiana V. Rychkova, Elena V. Kartasheva, Mariya A. Nazarova, Anna A. Kuzmina. The impact of secondary mineral formation on Na-K-geothermometer readings: a case study for the Valley of Geysers hydrothermal system (Kronotsky State Nature Biosphere Reserve, Kamchatka) ................................. 526

Geotechnical Engineering and Engineering Geology

     Victor I. Alexandrov, Anna M. Vatlina, Pavel N. Makharatkin. Substantiation and selection of the design parameters of the hydroficated equipment complex for obtaining backfill mixtures from current enrichment tailings .................................................................. 541

     Aleksandr E. Burdonov, Nikita D. Lukyanov, Vladislav V. Pelikh, Valery M. Salov. Application of the support vector machine for processing the results of tin ores enrichment by the centrifugal concentration method ............................................................................... 552

     Mikhail G. Vystrchil, Vladimir N. Gusev, Arseniy K. Sukhov. A method of determining the errors of segmented GRID models of open-pit mines constructed with the results of unmanned aerial photogrammetric survey ................................................................................ 562

     Alexander P. Gospodarikov, Ilia E. Revin, Konstantin V. Morozov. Composite model of seismic monitoring data analysis during mining operations on the example of the Kukisvumchorrskoye deposit of AO Apatit.................................................................................. 571

     Ilya M. Indrupskiy, Ildar I. Ibragimov, Timur N. Tsagan-Mandzhiev, Azat A. Lutfullin, Alexander P. Chirkunov, Ravil I. Shakirov, Yulia V. Alekseeva. Laboratory, numerical and field assessment of the effectiveness of cyclic geomechanical treatment on a tournaisian carbonate reservoir..................................................................................... 581

     Aleksey V. Kashnikov, Yuri V. Kruglov. Strategy of mine ventilation control in optimal mode using fuzzy logic controllers ........................................................... 594

     Vladimir A. Korshunov, Anton A. Pavlovich, Alexander A. Bazhukov. Evaluation of the shear strength of rocks by cracks based on the results of testing samples with spherical indentors . 606

     Anatoliy G. Protosenya, Nikita A. Belyakov, Maria A. Bouslova. Modelling of the stress-strain state of block rock mass of ore deposits during development by caving mining systems ......... 619

Economic Geology

     Alexey E. Cherepovitsyn, Nikita A. Tretyakov. Development of a new assessment system for the applicability of digital projects in the oil and gas sector .................................. 628


494

ISSN 2411-3336; е-ISSN 2541-9404





                JOURNAL OF MINING INSTITUTE




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Review article



            Wodginite as an indicator mineral of tantalum-bearing pegmatites and granites


Viktor I. ALEKSEEV
Saint Petersburg Mining University, Saint Petersburg, Russia


       How to cite this article: Alekseev V.I. Wodginite as an indicator mineral of tantalum-bearing pegmatites and granites. Journal of Mining Institute. 2023. Vol. 262, p. 495-508. EDN RJACLL. DOI: 10.31897/PMI.2023.19

       Abstract. In the composition of tantalum-niobates the tin-bearing wodginite group minerals (WGM) were found: wod-ginite, titanowodginite, ferrowodginite, ferrotitanowodginite, lithiowodginite, tantalowodginite, “wolframowodginite”. We reviewed the worldwide research on WGM and created a database of 698 analyses from 55 sources including the author's data. WGM are associated with Li-F pegmatites and Li-F granites. Wodginite is the most prevalent mineral, occurring in 86.6 % of pegmatites and 78.3 % of granites. The occurrence of WGM in granites and pegmatites differs. For instance, titanowodginite and “wolframowodginite” occur three times more frequently in granites than in pegmatites, whereas lithiowodginite and tantalowodginite do not appear in granites at all. The difference between WGM in granites and pegmatites is in finer grain size, higher content of Sn, Nb, Ti, W, and Sc; lower content of Fe³⁺, Ta, Zr, Hf; higher ratio of Mn/(Mn + Fe); and lower ratio of Zr/Hf. The evolutionary series of WGM in pegmatites are as follows: ferrowodginite ^ ferrotitanowodginite ^ titanowodginite ^ “wolframowodginite” ^ wodginite ^ tantalowodginite; in granites: ferrowodginite ^ ferrotitanowodginite ^ “wolframowodginite” ^ wodginite ^ titanowodginite. WGM can serve as indicators of tantalum-bearing pegmatites and granites. In Russia the promising sources of tantalum are deposits of the Far Eastern belt of Li-F granites containing wodginite.

       Keywords: wodginite group; titanowodginite; ferrowodginite; “wolframowodginite”; rare-metal lithium-fluoric granite; rare-metal pegmatite; tantalum; rare-metal deposits; typomorphism; isomorphism

       Acknowledgment. The study was funded by the Russian Foundation for Basic Research within the research project N 20-15-50064.

       Received: 22.08.2022         Accepted: 02.02.2023        Online: 20.04.2023         Published: 28.08.2023


     Introduction. The current development of metallurgy and battery industry determines steady growth in consumption of tantalum. The European Commission notes the crucial importance and the shortage of tantalum raw materials, as well as the uneven geographical distribution of its world reserves. Tantalum is on the list of strategic raw materials taken into account by the Decree of the President of the Russian Federation “On the application of special economic measures...” issued on 5 August 2022 under the sanctions regime. The increase in tantalum production is accompanied by changes in the economic geology of rare-metal raw materials. First, deposits of rare-metal Li-F granites in Egypt, China, and other countries are growing in industrial importance along with pegmatite deposits of Australia, Canada, and Brazil [1-3]. Second, economic significance of tin-tantalum ores, composed of cassiterite and wodginite, increases as well.
     Wodginite is the least studied industrial mineral of tantalum. We need to systematize empirical information about it. The latest reviews on the mineralogy of wodginite for pegmatite deposits date back to 1989-1992 [4, 5]. The study of wodginite in Russia is particularly relevant, as it has been described only in four regions between 1960 and 1980 [6-8]. The study of accessory minerals provides important information on the origin of igneous rocks, their formation conditions and their correlation features with magmatic complexes of different regions [9, 10]. Therefore, methods of local analysis of substances are the key issues [11, 12]. This article is a modern scientific review of worldwide studies on wodginite group minerals (WGM) since the discovery of wodginite in 1963. The scientific novelty of the work is to generalize the latest results achieved in the 21st century, refine

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This is an open access article under the CC BY 4.0 license

ида.и Journal of Mining Institute. 2023. Vol. 262. P. 495-508                               EDN RJACLL
© Viktor I. Alekseev, 2023                                                 DOI: 1O.31897/PMI.2023.19

earlier conclusions and analyze the possibility of using WGM as indicators of tantalum-bearing pegmatites and granites, as well as industrial sources of rare metals. We paid attention to Russian wod-ginite and used our own data on the Far East deposits.
     Current state of research of the wodginite group minerals. Main industrial sources of tantalum are represented by tantalite - columbite minerals, microlite group minerals, Ta-cassiterite, and wod-ginite. Over the century and a half span of studying tantalum-niobates, a wealth of material was accumulated; a coherent classification of Ta-Nb oxides was created. The Scopus abstract database contains 634 sources on the subject, whereas only 81 of them are related to wodginite. Wodginite (MnSnTa2O8) was first described as ixiolite in 1909 from a tantalum deposit in Wodgina, Australia [13]. In 1963, E.H.Nickel and coauthors discovered a similar mineral in lithium-caesium pegmatites at the Bernic Lake deposit in Canada and named it after the place of discovery [14].
     Currently wodginite is considered a title mineral of relatively rare tin-bearing tantalum-niobate minerals, which are included as accessories in the composition of rare-metal pegmatites (hereafter “pegmatites”) from Australia, Brazil, China, Central Africa, Canada, Europe, and other regions [1, 4, 15] (Table 1). During the development stage of classification, WGM were known from 37 occurrences [5]. After the discovery of wodginite-tantalum ores in the Bernic Lake mine in Canada, wodginite acquired the status of an industrial mineral. This has subsequently increased interest in WGM, and today more than 79 points of their occurrence are known [16]. We observe a gradual increase in the industrial importance of wodginite in the tantalum deposits of provinces such as Bor-borema in Brazil, Guarda-Belmonte in Portugal, Damara in Namibia, Kibara in DR Congo, Masvingo in Zimbabwe, Superior and Separation Rapids in Canada, Bastar-Malkangiri in India, Cathaysia in China, Balingup and Wodgina in Australia, Kalba-Narym in Kazakhstan, and others.
     In 20th century, wodginite was known only from pegmatites, but since 2002, there has been a growing flow of information on accessory WGM in rare-metal lithium-fluoric granites (hereafter granites) of Algeria (Ebelekan, Filfila), Egypt (Abu Dabbab, Nuweibi, Mueilha), Spain (Penouta), China (Yichun, Dajishan), the Czech Republic (Hub) [1, 3, 17] (Fig.1, Table 2). The reasons for the late discovery of WGM in granites are the insignificant size of these minerals and their similarity to tantalite. Tantalum-bearing granites that contain wodginite have been established in the Nubian-Arabian shield in Egypt, the Maghrebian thrust belt in Algeria and Morocco, the Iberian Massif in Spain, and Cathaysia in China.
     In Russia, WGM have not been studied enough: they were found only in pegmatites of the Kola Peninsula (Voron’i Tundry, Keivy), Eastern Sayan (Vishnyakovskoye, Malorechenskoye), the Urals (Taiginskoye) and Eastern Transbaikalia [18-20]. In granites from Russia, wodginite has been described only from the Voznesenskoye deposit (Primorye) [21, 22]. We established the presence of wodginite in the granites of the Kester deposit (Yakutia) [23].
     Actual material and methods. The review of wodginite studies used published data for the period 1963-2022 and author’s materials on rare-metal and tin deposits of the Far East of Russia and Egypt. Information on the composition, physical properties and structure of minerals is organized in the form of a summary database, which includes 470 analyses (44 sources) of WGM from pegmatites and 228 analyses (11 sources) of WGM from granites obtained mainly by the EPMA method. It should be noted that the actual number of analyses underlying the review is significantly larger, as we used representative analyses from arrays with volumes of tens and hundreds of samples from the publications. The article uses original author’s data obtained during the study of granites from the Arga-Ynnakh-Khay massif in Yakutia with the Sn-Ta Kester deposit and from the Abu Dabbab and Nuweibi massifs with Sn-Ta deposits in Egypt.
     The study of WGM, their occurrence statistics, composition and physical properties was assessed. A comparative analysis of parameters of identical minerals in pegmatites and granites was carried out. The data were statistically processed taking into account parameter distribution [24] using Microsoft Excel 2010 and Statistica 8.0 programs. The study of WGM properties for solving genetic problems was based on principles set out in [25].

496 ---------------------------------------------------------------------------------------------------
     This is an open access article under the CC BY 4.0 license

Journal of Mining Institute. 2023. Vol. 262. P. 495-508
© Viktor I. Alekseev, 2023

EDN RJACLL
DOI: 10.31897/PMI.2023.19

Table 1

Chemical composition (wt.%) of wodginite group minerals in rare-metal pegmatites of the world

Deposit                     N   MnO   FeO   SnO2  TiO2  Fe2O3 Ta2O5 Nb2O5 Li2O WO3  ZrO2 HfO2 CaO  Sc2O3 Source
                                                  Wodginite                                                    
Keivy, Russia               1   10.88 0.54  17.50 1.45  0.33* 62.94 4.92   -   1.07  -   -     -     -   [18]  
Kalba, Kazakhstan           1   10.91 3.06  10.26 0.81  3.23* 67.50 7.09   -    -    -   -     -     -   [6]   
Eastern Sayan, Russia       2   7.96  -     6.66  1.58  4.37  73.20 4.56   -    -    -   -    0.81   -   [7]   
Vishnyakovskoe, Russia      36  9.76  0.81  12.30 0.32  0.10* 71.03 3.06   -   0.00  -   -    0.07   -   [19]  
Challanpara, India          1   9.74  1.73  11.79 1.45  0.89* 67.96 3.06   -   0.68 1.31 0.00  -     -   [26]  
Seridozinho, Brazil         1   7.20  4.80  13.10 0.10  1.31* 68.40 3.50   -    -   1.50 -     -     -   [27]  
Peerless, USA               4   10.30 0.28  17.10 0.10  0.45  66.50 4.30   -    -        -     -     -   [28]  
Varutrask, Sweden           2   10.14 0.26  10.70 0.02    -   65.34 9.70   -   0.01 2.05 0.82 0.01   -   [29]  
Red Cross Lake, Canada      3   11.01 0.03  16.13 0.03    -   64.02 6.27   -   0.00 1.21 0.24 0.03   -   [30]  
Wodgina, Australia          1   10.70 -     13.00 1.40  0.80  68.60 4.00   -    -    -   -     -     -   [31]  
Muhembe, Rwanda             1   4.30  6.30  14.50 0.90  1.70  61.10 10.90 0.20  -   0.00 -     -   0.00  [15]  
Nanping, China              1   9.00  1.30  14.00 0.10  2.00  67.00 5.90  0.17  -   0.00 -     -   0.00  [15]  
Kariblb, Namibia            1   11.00 -     14.50   -     -   68.90 4.40   -    -        -     -   0.00  [15]  
Tahara, Japan               1   9.60  1.60  7.40  4.70  0.10  71.00 0.80   -   0.60 0.20 -     -   1.70  [15]  
Tanco, Canada               1   8.90  2.30  8.80  5.50  1.20  60.40 11.10 0.14  -   0.00 -     -     -   [15]  
Guarda-Belmonte, Portugal   3   6.88  7.70  10.73 4.01  2.96* 59.10 11.58  -    -    -   -     -     -   [32]  
La Viquita, Argentina       8   5.43  2.32  10.03 1.39  1.60  71.28 3.23  0.19 0.05 0.99 -    0.02 0.00  [33]  
Leggia valley, Switzerland  2   8.40  3.79  14.53 0.54  1.43* 68.50 3.04   -   0.84  -   -    0.00 0.00  [34]  
Emmons, USA                 3   9.63  1.64  16.44 0.32  0.54* 69.23 3.55  0.05  -    -   -           -   [35]  
Aclare, Ireland             1   7.73  4.89  12.78 1.18  1.53  64.35 8.65   -    -    -   -    0.09   -   [36]  
Viitaniemi, Finland         1   8.80  1.20  11.80 0.30    -   70.60 5.50   -    -    -   -    1.20   -   [37]  
Numbi, DR Congo             1   6.42  4.67  14.12 0.49  1.60  61.14 7.46   -   0.70 1.11 -           -   [38]  
Pusterwald, Austria         1   8.17  5.10  15.96 0.44  2.07* 59.75 9.81   -             -    0.82   -   [39]  
Annie Claim, Canada         2   10.84 1.01  14.83 0.07  0.00  62.62 7.25   -   0.11 1.85 0.45 0.01 0.00  [40]  
Bernic Lake, Canada         1   9.04  1.87  13.20 2.39  0.27* 70.05 1.35   -    -    -   -     -     -   [14]  
Govindpal, India            6   10.04 0.95  15.78 0.68  0.07* 65.60 4.95   -   0.17 0.35 -    0.05   -   [41]  
Nanping, China              2   9.64  0.84  15.83 0.25  1.36* 67.72 4.18  0.11 0.04      -         0.17  [42]  
Pendalras, India            12  8.87  2.67  12.99 0.93  0.92* 60.70 5.07   -   2.70 1.08 0.32 0.12   -   [26]  
Wodgina, Australia          1   10.47 1.34  8.92  0.00  0.96* 70.49 7.63   -    -    -   -    0.42   -   [13]  
Tin Mountain, USA           7   7.85  2.60  15.33 0.31  1.44  65.40 4.80   -    -    -   -     -     -   [43]  
Musselwhite, Canada         5   11.05 0.29  14.36 0.55  0.48* 68.08 3.84   -   0.30 0.99 -    0.07 0.15  [44]  
Rubellite Dyke, Canada      3   10.56 0.69  15.54 0.85  0.51* 68.03 3.31   -   0.14  -   -    0.02 0.18  [45]  
Separation Rapids, Canada   5   9.66  1.69  15.32 0.89  1.78  62.29 6.87  0.04 1.31  -   -     -   0.02  [46]  
Tanco Lower, Canada         164 8.89  2.05  13.10 2.50  1.12  64.60 6.18  0.07 0.06  -   -     -   0.15  [47]  
Herbb N 2, USA              4   8.13  3.30  12.30 3.65  0.45  67.18 5.25   -    -    -   -     -     -   [48]  
                                                  Titanowodginite                                              
Fonte del Plete, Italy      3   11.06 -     6.76  9.63    -   64.08 5.64   -   0.31  -   -     -     -   [49]  
Feio, Brazil                1   0.20  12.96 2.79  10.59 0.93* 68.07 5.71   -    -   0.26 -    0.00 0.29  [50]  
Nancy, Argentina            5   7.52  4.94  0.03  11.88 1.44  66.56 6.94   -   0.22  -   -    0.10   -   [51]  
Separation Rapids, Canada   2   8.59  4.30  7.75  8.68  1.00  54.95 14.29 0.00 0.07  -   -     -   0.05  [46]  
                                                  Ferrowodginite                                               
Keivy, Russia               1   0.87  17.81 10.88 0.39  7.23* 51.18 18.96  -    -    -   -    0.00   -   [18]  
Eastern Transbaikal, Russia 1   6.94  5.26  9.44  0.93  7.89  63.16 7.21   -    -    -   -     -     -   [8]   
Cap de Creus, Spain         1   5.25  6.29  11.82 0.53  1.92  64.90 6.63   -    -    -   -     -     -   [52]  
Borborema, Brazil           3   3.16  11.07 12.40 0.82  3.01* 60.53 11.21  -    -   0.73 -    0.00 0.16  [53]  
Seridozinho, Brazil         1   3.50  9.10  13.10 0.10  1.13* 59.40 12.80  -    -   1.50 -     -     -   [27]  
La Viquita, Argentina       3   5.43  2.32  10.03 1.39  1.60  71.28 3.23  0.19 0.05 0.99 -    0.02 0.00  [33]  
Numbi, Congo                1   5.23  6.33  12.33 2.10  2.06  56.37 10.91  -   1.69 0.69 -     -     -   [38]  
Annie Claim, Canada         2   5.05  6.73  11.63 0.02  0.50  59.58 8.71   -   0.67 4.95 1.18 0.03 0.00  [40]  
Pilawa Gorna, Poland        4   3.13  9.05  12.50 1.63  2.13  55.21 13.86  -   2.06 0.51 -     -   0.12  [54]  
Nanping, China              6   5.36  5.94  14.54 1.16  1.72  62.13 8.08  0.01 0.02  -   -     -   0.16  [42]  
Separation Rapids, Canada   4   3.00  9.13  13.02 2.44  2.32  54.85 13.53 0.01 1.58  -   -     -   0.03  [46]  
Nyanga 2, Uganda            1   6.00  6.70  8.60  2.30  1.63* 68.00 7.70   -    -    -   -     -     -   [55]  
Sukula, Finland             3   3.00  7.00  10.00 3.00  0.23* 62.00 12.67  -    -    -   -     -     -   [56]  

Ferrotitanowodginite

San EHas, Argentina       9 2.48  8.96  3.04 7.31   1.76 67.97 7.32   -   0.03  0.09 - 0.01 0.00 [57]
La Calandria, Argentina   7 4.58  7.29  4.57 7.90   4.31 44.04 23.62  -   1.24  0.62 - 0.02  -   [58]
Nancy, Argentina          3 3.95  8.07  0.05 9.20   2.70 71.00 4.12   -   0.07   -   - 0.18  -   [51]
Separation Rapids, Canada 2 2.57  10.39 8.23 8.37   1.05 62.99 11.97 0.00 0.03   -   -  -   0.05 [46]
                                        “Wolframowodginite”                                          
Separation Rapids, Canada 5 11.57 1.23  9.37 0.70   3.75 46.27 10.39 0.06 16.01  -   -  -   0.05 [46]

       Notes. The average contents are given according to sources (N - number of analyses). For samples of more than 10 tests, median contents are given [24]. Dash - no data. Fe2O3* - calculated value.

497

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Journal of Mining Institute. 2023. Vol. 262. P. 495-508
© Viktor I. Alekseev, 2023

EDN RJACLL
DOI: 10.31897/PMI.2023.19

Fig.1. Wodginite (Wdg), titanowodginite (Twdg) and cassiterite (Cst) in albitic (Ab) rare-metal granite from the Nuweibi deposit in Eastern Egypt.
Image in backscattered electrons

     Classification, structure and properties of minerals of the wodginite group. According to the current classification of the International Mineralogical Association (IMA) [16], the following minerals of the wodginite group are distinguished: wodginite (MnSnTa2O8) [14]; titano-wodginite (MnTiTa2O8) [5]; ferrowodginite (FeSnTa2O8) [5]; ferrotitanowodginite (FeTiTa2O8) [57]; lithiowodginite (LiTaTa2O8) [59]; tanta-lowodginite ((Mn0.5^0.5)TaTa?O8) [35]; and “wolframowodginite” (unapproved mineral species) (MnTi(Ta,W)2O8) [46] (Tables 1, 2). Varieties of WGM differ in the ratio of major and minor elements (> 0.01%): W, Fe³⁺, Ca, Sc, Zr, Hf.
The history of decoding the structure of wod-ginite is presented in article [31]. Three positions of

cations in hexagonal coordination are distinguished: A (Mn), B (Sn), and C (Ta). Oxygen octahedra form zigzag chains with edge joints, connected in rhythmically repeating layers of three types: ABA -- CCC - BAB - CCC. General distribution of cations: ABC2O8 (Z = 4). Thus, the crystal lattice of wodginite is a derivative of a disordered lattice of ixiolite and more ordered than the columbite-tantalite lattice AB2O6, consisting of layers of octahedra ABB. Wodginite can be considered as a maximally ordered ixiolite with an enlarged fourfold elementary cell [60-62]. This is confirmed experimentally: ixiolite containing SnO2 (up to 19.5 %) and TiO2 (up to 15.8 %) when heated turns into wodginite. The type of wodginite structure is intermediate between layered and framework depending on the ratio of cations in the formula ABC2O8, which is reflected in the structure of lithiowodginite, where B = C and the composition of the mineral is described by the formula АВ3O8 [59].


Table 2

Chemical composition (wt.%) of wodginite group minerals in rare-metal granites of the world

Deposit               N   MnO   FeO   SnO2  TiO2  Fe2O3   Ta2O5   Nb2O5 Li2O  WO3  ZrO2 HfO2 CaO  Sc2O3    Source    
                                                    Wodginite                                                        
Kester, Yakutia       12  9.95  3.36  11.46 1.23  1.95*   58.93   12.72  -   1.76   -    -    -   -     Author’s data
Abu Dabbab, Egypt     128 10.63 1.80  13.60 2.27  1.21*   62.63   7.97   -     -    -    -    -   -     Author’s data
Penouta, Spain        6   6.51  4.59  15.18 0.10  1.48    62.62   6.92   -   0.33  0.46 0.67 0.05 0.13      [63]     
Greer Lake, Canada    2   10.95 0.00  15.10 0.10  0.65    67.75   3.90   -     -    -    -    -   -         [64]     
Nuweibi, Egypt        3   7.38  5.14  13.23 0.38  1.45*   62.50   8.93   -     -   0.65 0.72  -   -         [65]     
Ebelekan, Algeria     4   10.60 1.07  11.98 3.02  1.15    59.86   10.36 0.01 0.81   -    -   0.06 0.30      [66]     
Yichun, China         5   10.16 0.82  15.46 0.76  1.18    65.47   4.87   -   0.27   -    -    -   0.45      [17]     
Nuweibi, Egypt        43  10.25 1.43  13.56 0.42  1.19*   65.95   4.96   -     -    -    -    -   -          [3]     
Gedongping, China     2   10.45 3.61  10.36 1.73  3.25*   64.57   6.91   -   1.16   -    -    -   0.00      [67]     
Dajishan, China       2   11.54 1.27  9.52  1.05  1.66*   57.95   14.08  -   2.12   -    -    -   -         [68]     
Songshugang, China    3   4.12  9.90  6.38  7.31  1.77*   53.89   15.22 0.03 1.93   -    -    -   0.21      [69]     
                                                  Titanowodginite                                                    
Voznesenskoye, Russia 1   7.90  3.70  6.90  10.90   -     51.20   16.80  -   1.90   -    -    -   -         [21]     
Ebelekan, Algeria     1   9.97  2.11  7.90  8.13  0.26    57.13   11.76 0.03 1.48  0.00 0.00 0.00 0.36      [66]     
Yichun, China         5   11.07 0.54  4.52  7.66  0.61    65.39   9.58   -   0.19   -    -    -   0.47      [17]     
                                                  Ferrowodginite                                                     
Hub, Czech Republic   3   5.62  6.66  9.33  2.58  1.83    57.36   10.91  -   3.36  0.29  -    -   0.16      [70]     
Songshugang, China    3   4.98  11.37 5.90  4.59  3.75*   41.22   28.03 0.02 2.30   -    -    -   0.26      [69]     
                                              Ferrotitanowodginite                                                   
Gedongping, China     2   4.43  9.29  8.19  5.01  2.18*   54.91   12.75  -   2.10   -    -    -   0.00      [67]     
Nuweibi, Egypt        2   6.30  6.20  11.73 3.48  0.73*   58.75   13.00  -     -    -    -    -     -   Author’s data
                                              “Wolframowodginite”                                                    
Songshugang, China    3   8.33  8.85  4.35  1.68  0.43*   38.97   17.98 0.21 18.39  -    -    -   0.79      [69]     

* See notes to Table 1.

498

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EDN RJACLL                                                 Journal of Mining Institute. 2023. Vol. 262. P. 495-508 идаи
DOI: 10.31897/PMI.2023.19                                                        © Viktor I. Alekseev, 2023

     Isomorphism of the WGM. Polyelemental isomorphism in three positions of the crystalline structure A, B and C determines the difference between mineral species of WGM: A = (Mn²⁺, Fe²⁺, Li, Ca, □), B = (Sn⁴⁺, Ti, Fe³⁺, Ta, Sc, Zr), C = (Ta, Nb, W⁶⁺) [4, 15, 60]. Position A is occupied in wodginite and titanowodginite (> 50 %) by Mn cations which are replaced by Fe²⁺ cations in appropriate conditions to form ferrowodginite and ferrotitanowodginite [15]. The characteristic feature of the low-valent position A is the presence of a significant number of vacancies that compensate for the excess charges of high-valent cations (Ta⁵⁺, W⁶⁺) populating positions B and C in tantalowodginite, lithio-wodginite and “wolframowodginite” [15, 29, 63] (Tables 1, 2). Position B in WGM is crystallographically unstable due to competition between heterovalent cations Sn⁴⁺, Ti⁴⁺, Fe³⁺, Ta⁵⁺, Sc³⁺, Zr⁴⁺. The composition of the octahedral layer B is of great importance for the classification of WGM and genetic studies [59, 46, 60]. Tin plays a major crystallographic role - an activator of the polymorphic transformation of the disordered ixiolite structure into an ordered wodginite structure. Upon heating ixiolite with SnO2 content < 0.2 %, rhombic columbite-tantalite is formed, and with SnO2 > 9-10 % - monoclinic wodginite [59]. Tin substitutes in the wodginite structure are Ti, Fe³⁺, Ta, Sc, Zr [8, 71] (Tables 1, 2).
     In tantalum-niobates, titanium usually plays a large role but in WGM the isomorphism Ti ^ Ta is limited. The most effective way to incorporate Ti into the structure is Ti⁴⁺ ^ Sn⁴⁺ with the formation of titanowodginite [15, 60] (Tables 1, 2, Fig.1). The main scheme of isomorphism in the series tantalite ^ wodginite, titanowodginite ^ microlite: A[Fe, Mn]²⁺ + 2С[Nb, Ta]⁵⁺ ^ 3B[Sn, Ti]⁴⁺ [27, 28]. Wodginite and titanowodginite differ sharply in concentration of SnO2 and TiO2, indicating possibly a miscibility gap between WGM with compositions (Fe, Mn)SnTa2O8 and (Fe, Mn)TiTa2O8 but requiring further study [17].
     Since wodginite is formed under oxidizing conditions, a small part of iron in it is in the form of Fe³⁺ cations [4, 70, 71] (Tables 1, 2). The Fe³⁺/Fe²⁺ ratio in wodginite has a higher value than in tantalite [41]. Sn⁴⁺ and Fe³⁺ cations are interchangeable in the structure of wodginite and in the absence of tin, its role is played by Fe³⁺ [8, 61, 62]. In iron-bearing varieties of WGM - ferrowodginite, ferrotitanowodginite, “wolframowodginite” - electron neutrality is achieved by occupying position B of a part of tantalum cations: 2B[Sn⁴⁺] ^ B[Fe³⁺] + B[Ta⁵⁺] [15, 59].
     In all types of pegmatites, especially tantalum wodginite and lithiowodginite, there is an excess of cations (Ta + Nb) in position C, reaching up to 3.7 cations per formula unit [15, 60]. Ta is introduced into position B (Table 3) according to the scheme: 2BTa⁵⁺ + A□ ^ AMn²⁺ + 2BSn⁴⁺ [41]. In lithiowodginite, the excess of positive charge of Ta⁵⁺ cations in position B is regulated by the mechanism: A [Mn²⁺] + B [Sn⁴⁺] ~ A [Li⁺] + B [Ta⁵⁺] [15].
     In position C, Ta and Nb dominate, forming layers of NbO6 and TaO6 octahedra, the most stable element of the layered structure of pegmatites. The predominance of undistorted Ta-O octahedra is the key to the highly ordered structure of wodginite [59]. Isomorphism Ta ^ Nb is limited by a value of 8 cations per formula unit [15, 60]. Tungsten can settle in position C [59]. The structural similarity between wodginite and wolframite has been experimentally confirmed [72]. The presence of a significant impurity WO3 in wolframite and its correlation with (FeO + Fe2O3) content has been noted in granites [63, 68] and pegmatites [26, 46]. The hypothesis has been put forward about the existence of “wolframowodginite”, described in pegmatites of the Separation Rapids deposit in Canada [46] and in granites of Songshugang deposit in China [69]. For iron-bearing varieties of WGM, a mechanism for settling tungsten has been proposed: B [Sn⁴⁺] + C [Ta⁵⁺] ^ B [Fe³⁺] + C [W⁶⁺]; for manganese-bearing varieties: B [Sn⁴⁺] + 2 C [Ta⁵⁺] ^ B [Mn²⁺] + 2 C [W⁶⁺]; for lithium-bearing wodginite: 2А [Li⁺] + + 2A[Mn²⁺] ^ C[W⁶⁺] [46] (see Tables 1, 2).
     Physical properties of WGM. The properties of WGM have been studied mainly on the example of wodginite from pegmatites. It is represented by hypidiomorphic prismatic and wedge-shaped crystals of dark reddish-brown or black color; its lustre is greasy and semi-metallic. Often the mineral forms irregular segregations in the interstices of feldspar, albite and mica or microinclusions in columbite-tantalite, cassiterite, microlite. The sizes of WGM crystals in pegmatites vary from 2-10 microns in microinclusions to 13 cm in albite aggregates, averaging ~ 1 cm. In granites, the grain sizes are significantly smaller: 1-100 microns, on average 27 microns.

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Journal of Mining Institute. 2023. Vol. 262. P. 495-508
© Viktor I. Alekseev, 2023

EDN RJACLL
DOI: 10.31897/PMI.2023.19

Table 3
Distribution of main cations in the structure of wodginite group minerals in rare-metal pegmatites and granites of the world

Cation in position     Wodginite        T itanowodginite     Ferrowodginite     F errotitanowodginite    
                   Ме (612) Min Max IQR Ме (18) Min Max IQR Ме (36) Min Max IQR Ме (17) Min    Max   IQR

Pegmatites

A: Mn 0.86 0.38 1.03 0.20 0.66 0.02 0.94 0.29 0.35 0.07 0.67 0.22 0.28 0.20 0.37 0.14
Fe2+  -    -    0.42 0.11 -    -    1.05 0.35 -     -   0.93 0.61 -    -    -    0.00
Li    -    -    0.04 0.00 -    -     -   0.00 -     -   0.01 0.00 -    -    -    0.00
B: Sn 0.58 0.30 0.75 0.15 0.19 -    0.30 0.20 0.51 0.36 0.62 0.10 0.15 -    0.30 0.11
Ti    0.06 -    0.42 0.10 0.75 0.62 0.87 0.09 0.09  -   0.23 0.14 0.58 0.57 0.72 0.05
Fe3+  0.07 -    0.37 0.10 0.07 -    0.11 0.03 0.16  -   0.68 0.08 0.17 0.07 0.31 0.12
Ta    0.20 0.09 0.50 0.09 0.05 0.02 0.08 0.02 0.22 0.15 0.34 0.11 0.20 0.09 0.25 0.04
C: Ta 1.79 1.51 1.77 0.21 1.71 1.41 1.71 0.10 1.49 1.22 1.63 0.29 1.55 1.05 1.75 0.45
Nb    0.24 0.04 0.52 0.16 0.28 0.25 0.62 0.13 0.52 0.24 0.85 0.23 0.42 0.19 1.02 0.33
W     -    -    0.08 0.00 -    -    0.01 0.00 -     -   0.05 0.02 -    -    0.03 0.01

Granites

A: Mn 0.93 0.33 1.03 0.17 0.82 0.62 0.93 0.16 0.44 0.39 0.50 0.06 0.46 0.38 0.54 0.08
Fe2+  0.06 -    0.66 0.12 -    -    0.28 0.14 0.30  -   0.61 0.30 0.54 0.46 0.62 0.08
Li    -    -    0.01 0.00 -    -    0.01 0.00 -     -    -   0.00 -    -    -    0.00
B: Sn 0.56 0.24 0.67 0.16 0.25 0.18 0.31 0.06 0.30 0.22 0.39 0.09 0.40 0.33 0.47 0.07
Ti    0.08 0.01 0.53 0.11 0.59 0.57 0.75 0.09 0.26 0.20 0.32 0.06 0.32 0.26 0.38 0.06
Fe3+  0.12 0.05 0.26 0.03 0.02 -    0.05 0.02 0.20 0.14 0.26 0.06 0.11 0.06 0.17 0.06
Ta    0.23 0.11 0.36 0.07 0.06 0.02 0.19 0.08 0.25 0.25 0.25 0.00 0.17 0.15 0.19 0.02
C: Ta 1.58 1.29 1.69 0.07 1.46 1.26 1.57 0.24 1.08 0.78 1.39 0.31 1.39 1.36 1.41 0.04
Nb    0.40 0.20 0.66 0.22 0.52 0.43 0.70 0.14 0.84 0.52 1.16 0.32 0.59 0.58 0.59 0.00
W     0.01 -    0.06 0.04 0.04 -    0.05 0.02 0.07 0.05 0.09 0.02 0.03 -    0.06 0.03

       Notes. The formula coefficients of cations (f.c.) in positions A, B, C, calculated for the formula ABC2O8 are given. Dash - f.c. < 0.005. Me - median value of f.c. (in parentheses - number of samples). Min and Max - minimum and maximum values of f.c. IQR - interquartile range of f.c. [24].

     The syngony of WGM is monoclinic (C2/c). Simple and polysynthetic twins are characteristic. Cleavage is imperfect. Density ranges from 7.03 to 7.81 g/cm³; hardness is between 5.5 and 6. Optical properties: Np = 2.14-2.20, Ng = 2.23-2.27, Д = 0.07-0.09, (+), c:Ng = 26°. Under the microscope, it shows pleochroism from light yellow to reddish-brown; has a concentric-zonal and sectoral coloration [4, 7, 16].
     Minerals of the wodginite group — indicators of tantalum-bearing pegmatites and granites. Parent rocks and paragenesis of WGM. In the past two decades, researchers have identified two types WGM with industrial application in tantalum-bearing pegmatites and granites. This has prompted the investigation of the typomorphic features of these WGM in relation to their host rocks. Wodginite and other WGM occur as accessory minerals in rare-metal lithium-mica pegmatites of the Li-Cs-Ta geochemical type (LCT pegmatites) [29, 73]. Given the important role of fluorine in rare-metal pegmatite mineralization [29, 30, 69], parent rocks with WGM can be called lithium-fluoric pegmatites. Intrusive and exocontact bodies of pegmatites at deposits such as Wodgina (Australia), Bernic Lake (Canada), Koktogai (China), Bikita (Zimbabwe), Varutrask (Sweden), Vishnyakovskoe (Russia) and others are located on crystalline shields, in Caledonian and Hercynian folded structures and have Precambrian or Paleozoic age [1, 4, 7]. Mesozoic and Cenozoic pegmatites containing wodginite are also found [34, 35].
     Minerals of the wodginite group are concentrated in lepidolite- and muscovite-albite aggregates of intermediate zones, less often in quartz cores and miarolitic cavities of pegmatites. The following accessory and industrial minerals are observed in the composition of pegmatites: ambligonite-mon-tebrasite, pollucite, spodumene, petalite, garnet (spessartine-almandine), tourmaline (schorl-elbaite), beryl, topaz, lithiophilite, triphylite, triplite, eosphorite, eucryptite, chrysoberyl, ilmenite, zircon, thorite, uraninite, monazite, xenotime, Be-silicates (bertrandite, bavenite, milarite, helvine), sulfides 500 -------------------------------------------------------------------------------------------------

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EDN RJACLL                                                 Journal of Mining Institute. 2023. Vol. 262. P. 495-508 идаи
DOI: 10.31897/PMI.2023.19                                                        © Viktor I. Alekseev, 2023

(arsenopyrite, lollingite, herzenbergite, stannite, kesterite, molybdenite). Ta-cassiterite, apatite-(CaF), Hf-zircon and tantalum-niobates: tantalite-(Mn), columbite-(Mn), ixolite, minerals of the microlite group, tapiolite are constant companions of WGM. Other Ta-Nb oxides such as Ta-rutile, ilmenorutile, rynersonite, fersmite, euxenite-(Y), polycrase-(Y), tantite, simpsonite, uranmicrolite, stibiomicrolite, pyrochlore, samarskite, fergusonite are occasionally encountered. Some companion minerals (cassiterite, tapiolite, minerals of the microlite group, minerals of the tantalite - columbite series, and others) accompany WGM by replacing them [1, 43, 47]. Parallel and irregular intergrowths of WGM with tapiolite [27, 47, 51], rhythmically-zonal intergrowths with tantalite-(Mn) [32, 37, 45] are described; rims and inclusions of wodginite in Ta-rutile [51, 53, 58] are common. The co-occurrence of wodginite and other WGM - titanowodginite, ferrowodginite, tantalowodginite, ferrotitano-wodginite - is not uncommon. It has been described in pegmatites of Argentina (San EHas, La Calandria, Nancy), Brazil (Roncadeira, Seridozinho), India (Govindpal), Canada (Bernic Lake, Separation Rapids, Peerless, Annie Claim), China (Nanping), DR Congo (Numbi), Poland (Pilawa Gorna) and USA (Emmons) [1, 40, 46]. The relationship between WGM species is poorly studied.
     Wodginite occurs as inclusions in cassiterite pegmatites that reflect the composition of impurities in the host mineral. This suggests that wodginite-cassiterite solid solution is breaking down [2, 32, 54]. Wodginite in cassiterite is xenomorphic, predominantly homogeneous; inclusions are found along networks of tantalum-enriched zones separated by depleted cassiterite zones [40]. Submicro-scopic (< 0.1 pm) segregations of tantalates (ferrowodginite, tapiolite-(Fe), columbite-(Mn) - products of the breakdown of the discredited “staringite” solid solution) are described in cassiterite [53]. The growth zonality from the core to the periphery of Ta, Mn, Sn, Nb, Fe and Ti content serves as an indicator of primary accessory wodginite [32, 59, 66].
     In recent years, WGM has been found in tantalum-bearing granites of Li-F geochemical type at deposits in Nuweibi (Egypt), Yichun (China), Penouta (Spain), Voznesenskoye (Russia), etc. (Fig.1). The granites form small Phanerozoic intrusions in Hercynian and Mesozoic folded formations [65, 69, 74]. Minerals of the wodginite group are part of light-colored quartz-microcline-albite aggregates with a “snowball” structure including topaz, fluorite, spessartine, tourmaline, beryl, amblygonite-montebrasite, and others. Accessory minerals are constant companions of wodginite in granites: columbite-(Mn), tantalite-(Mn), Ta-cassiterite, microlite, apatite-(CaF), Hf-zircon. This association sometimes includes tapiolite-(Fe), stibiotantalite, wolframite, monazite, xenotime, pyrophanite, U-thorite, uraninite, euxenite, polycrase-(Y), Fe and Mn oxides, sulfides (pyrite, galena, sphalerite, bismuthinite). The combination of wodginite and titanowodginite in granites is quite rare [17, 66, 67] (Fig.1). The same situation applies to wodginite, ferrowodginite and “wolframowodginite” [69]. Crystal aggregates (inclusions, overgrowth, etc.) of WGM with cassiterite and tantalite-(Mn) are typical of granites [3, 75, 76]. Minerals of the wodginite group form rims in tantalite-(Mn) [65] and Ta-rutile [21]; development of wodginite along the growth surfaces of Ta-rutile has been described, which emphasizes a sectoral structure of the latter [74].
     Thus, WGM are associated with Li-F pegmatites and Li-F granites that are part of similar parageneses: Ta-cassiterite, apatite-(CaF), Hf-zircon, tantalite-(Mn), columbite-(Mn), ixolite, minerals of microlite group, tapiolite, and WGM. An assessment of the relative occurrence of WGM based on literature data showed that wodginite predominates significantly in pegmatites: wodginite - 86.6 %; ferrowodginite - 6.4 %; titanowodginite - 2.4 %; ferrotitanowodginite - 2.8 %; “wolframowodgi-nite” - 0.9 %; tantalowodginite - 0.9 %; lithiowodginite - 0.2 %. The occurrence of WGM in granites is noticeably different. With a leading role of wodginite in granites, titanowodginite and “wolf-ramowodginite” are three times more common in granites, and lithiowodginite and tantalowodginite are not found at all: wodginite - 78.3 %; titanowodginite - 7.6 %; ferrowodginite - 6.5 %; ferrotitano-wodginite - 4.4 %; “wolframowodginite” - 3.3 % (Fig.2). In general, among WGM, wodginite is the most common: 86.6 % in pegmatites and 78.3 % in granites.

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Journal of Mining Institute. 2023. Vol. 262. P. 495-508
© Viktor I. Alekseev, 2023

EDN RJACLL
DOI: 10.31897/PMI.2023.19

Fig.2. Relative occurrence of minerals of the wodginite group in rare-metal pegmatites (WP) and granites (WG) of the world: Fwdg - ferrowodginite, Ftwdg - ferrotitanowodginite, Wwdg - “wolframowodginite”, Ttwdg - tantalowodginite, Lwdg - lithiowodginite

      Chemical composition of minerals of the wod-ginite group in pegmatites and granites. When comparing wodginite minerals in pegmatites and granites, their chemical composition is the most informative. The main components of wodginite are Ta, Sn, Nb, Mn, Fe²⁺, Ti, Li, W. The most important impurity elements (> 0.01 %) are Ca, Sc, Zr, Hf (see Tables 1, 2). Based on a database, the composition of mineral species of the wodginite was calculated (Tables 3, 4). Data on small concentrations of non-formulaic elements - F, Na, Mg, Al, Si, Zn, As, Sr, Y, Sb, REE, Pb, Bi, Th, U [16], that could be the result of microlite substitution [46, 51, 58], capture of mineral inclusions by microprobe and other analytical errors [3, 26, 65], were not taken into account in the calculations. Our review shows a satisfactory correspondence of published compositions of wodginite minerals (see Tables 1 and 2) to the


classification of MMA minerals [16] (Fig.3). Thre trends in the symbate changes in atomic quantities


of Ta and Mn cations of wodginite during differentiation of pegmatites and granites have been established. A series of wodginite evolution in pegmatites is as follows: ferrowodginite ^ ferrotitanowodginite ^ titanowodginite ^ “wolframowodginite” ^ wodginite ^ tantalowodginite. In granites it is as follows: ferrowodginite ^ ferrotitanowodginite ^ “wolframowodginite” ^ wodginite ^ titano-wodginite. It is characteristic that the composition points of the iron-bearing wodginite species occupy the field of mixing gap between tapiolite-(Fe) and tantalite-(Fe) (Fig.4), which is noted in article [53].


Table 4

Variations of main components in minerals of the wodginite group in rare-metal pegmatites and granites of the world

Component     Wodginite        T itanowodginite      Ferrowodginite      F errotitanowodginite   “Wolframowodginite”   
          Ме (612) Min   Max   Ме (18) Min   Max    Ме (36)  Min   Max   Ме (17)   Min   Max     Ме (7) Min     Max   
                                                   Pegmatite   s                                                      
MnO       9.19     4.30  12.40 7.73    0.20  11.29   4.22    0.67  6.94   3.73    0.67   7.10    10.74  8.55    16.54 
FeO       1.39     0.00  10.86 4.86    0.00  12.96   7.40    0.54  17.81  7.34    5.43   10.91    0.00  0.00    3.10  
SnO2      13.58    6.22  19.20 2.79    0.00  8.65  12.54     8.13  18.80  5.89    0.00   8.94     8.10  4.85    17.50 
TiO2      0.49     0.00  5.50  10.62   7.52  12.95   1.29    0.01  6.48   7.00    5.77   12.99    0.08  0.05    1.80  
Fe2O3     0.00     0.00  4.72  1.02    0.00  2.19    1.62    0.00  7.89   2.61    0.44   7.83     2.58  0.33    7.05  
Ta2O5     67.17    55.55 85.04 65.18   53.68 68.95 60.13     48.78 68.00 49.38   38.90   75.02   44.55  34.67   62.94 
Nb2O5     4.62     0.00  14.47 6.64    4.08  15.66 10.33     3.83  18.96 19.77    2.78   26.72    7.27  4.00    17.97 
Li2O      0.00     0.00  0.27  0.00    0.00  0.00    0.00    0.00  0.11   0.00    0.00   0.11     0.00  0.00    0.16  
WO3       0.00     0.00  3.82  0.14    0.00  0.58    0.00    0.00  3.25   0.62    0.00   2.42    12.54  1.07    34.63 
                                                   Granites                                                           
MnO       10.28    3.95  12.55 11.04   7.90  11.30   5.36    4.27  6.15   5.32    4.34   6.49     7.77  5.93    11.29 
FeO       1.59     0.00  10.46 0.57    0.36  3.70    9.11    5.46  11.91  7.85    5.92   9.36     8.76  7.19    10.61 
SnO2      13.58    4.50  17.31 5.05    3.73  7.90    7.47    3.23  11.48  9.53    6.97   13.80    3.77  0.86    8.42  
TiO2      1.55     0.00  7.55  7.92    7.12  10.90   3.14    1.83  6.20   4.30    2.41   5.97     0.79  0.79    3.45  
Fe2O3     0.00     0.00  3.52  0.68    0.00  0.72    0.82    0.00  1.97   0.00    0.00   0.00     0.00  0.00    0.00  
Ta2O5     63.21    47.32 71.00 67.86   51.20 66.04 53.95     31.10 58.47 57.36   53.50   59.09   35.33  34.69   46.89 
Nb2O5     7.63     1.20  20.94 10.14   8.07  16.80 14.75     9.97  38.59 13.00   11.77   13.72   19.89  13.49   20.57 
Li2O      0.00     0.00  0.09  0.00    0.00  0.03    0.00    0.00  0.06   0.00    0.00   0.00     0.18  0.15    0.29  
WO3       0.00     0.00  3.33  0.22    0.02  1.90    2.84    1.30  4.42   0.77    0.00   2.65    18.03  13.22   23.93 

Notes. Ме - median value (in parentheses - number of samples); Min and Max - minimum and maximum content values, wt.%.

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