Fredrikssonite from Fumarolic Exhalations of the Tolbachik Volcano (Kamchatka, Russia), its Crystal Structure and Chemical-Genetic Features

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription or Fee Access

Abstract

Fredrikssonite, a Mn3+-dominant oxoborate of the ludwigite group, has been found in exhalations of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Earlier this mineral was known only in Mn-enriched skarnoids of the Filipstad ore district in Sweden. In the Arsenatnaya fumarole, Fredrikssonite occurs as reddish-rufous long-prismatic and acicular crystals up to 0.05 mm long in sublimate incrustations formed at temperatures not lower than 550 °C, in association with anhydrite, minerals of the berzelite-schäferite series, svabite, tilasite, calciojohillerite, magnesioferrite, hematite, Mn³⁺-containing ludwigite, rhabdoborite-group borates, diopside, forsterite, and powellite. Tolbachik fredrikssonite is represented by the Fe3+-richest variety known today, almost free of Fe2+ and Mn2+. Its chemical composition (wt.%): 40.96 MgO, 0.28 CuO, 26.57 Mn2O3, 13.03 Fe2O3, 17.78 B2O3, 1.41 As2O5, total 100.63; the empirical formula calculated based on 5 O atoms per formula unit is: (Mg1.97Cu0.01)∑1.98(Mn3+0.65Fe3+0.33)∑0.99[B0.99As0.02O3]O2. The parameters of the orthorhombic (space group Pbam) unit cell are: a = 9.2078(12), b = 12.4458(13), c = 2.9812(3) Å, V = 341.64(7) Å3. The crystal structure of fredrikssonite from the Arsenatnaya fumarole is solved on a single crystal (R = 6.95%); it is isostructural to other members of the ludwigite group. The formation conditions of Mn3+-rich oxoborates of this group are discussed.

About the authors

M. O Bulakh

Lomonosov Moscow State University

Email: aregon27@mail.ru
Faculty of Geology Moscow, Russia

S. N Britvin

St Petersburg State University

Email: aregon27@mail.ru
St Petersburg, Russia

N. V Zubkova

Lomonosov Moscow State University

Email: aregon27@mail.ru

Faculty of Geology

Moscow, Russia

V. O Yapaskurt

Lomonosov Moscow State University

Email: aregon27@mail.ru

Faculty of Geology

Moscow, Russia

A. A Agakhanov

Fersman Mineralogical Museum RAS

Email: aregon27@mail.ru
Moscow, Russia

L. P Anikin

Institute of Volcanology and Seismology

Email: aregon27@mail.ru
Petropavlovsk-Kamchatsky, Russia

I. V Pekov

Lomonosov Moscow State University

Author for correspondence.
Email: aregon27@mail.ru

Faculty of Geology

Moscow, Russia

References

  1. Alexandrov S. M. Geochemistry of Boron and Tin in Deposits of the Magnesian-Skarn Formation. Moscow: Nauka, 1982. 291 p.
  2. The Great Tolbachik Fissure Eruption (eds. S. A. Fedotov and Y. K. Markhinin). New York: Cambridge University Press, 1983. 341 p.
  3. Belskaya N. A., Kazak N. V., Vasiliev A. D., Eremin E. V., Moshkina E. M., Velikanov D. A., Bezmaternykh L. N., Gavrilkin S. Yu., Ovchinnikov S. G. Structural diversity and phase transitions in borates with mixed valence Mg2-xMn1+xBO5 (0.0 < x < 0.4). JEPT Letters. 2024. Vol. 120. P. 509—516 (in Russian).
  4. Bulakh M. O., Pekov I. V., Chukanov N. V., Yapaskurt V. O., Koshiyakova N. N., Britvin S. N., Sidorov E. G. Extremely fluorine-rich fluoborite from fumarolic exhalations of the Tolbachik volcano (Kamchatka). Zapiski RMO (Proc. Russian Miner. Soc.). 2021a. Vol. 150. N 2. P. 42—56 (in Russian, English translation: Geol. Ore Deposites. 2022a. Vol. 64. N 7. P. 432—441).
  5. Bulakh M. O., Pekov I. V., Koshiyakova N. N., Sidorov E. G. Ludwigite and yuanfuliite from fumarolic exhalations of the Tolbachik volcano, Kamchatka, Russia. Zapiski RMO (Proc. Russian Miner. Soc.). 2021b. Vol. 150. N 6. P. 67—87. (in Russian, English translation: Geol. Ore Deposites. 2022b. Vol. 64. N 8. P. 607—621).
  6. Bulakh M. O., Pekov I. V., Koshiyakova N. N., Nazarova M. A. Basalt alteration in high-temperature oxidizing-type fumaroles at the Tolbachik volcano (Kamchatka, Russia). Part 1. Processes and products of olivine alteration. Zapiski RMO (Proc. Russian Miner. Soc.). 2023. Vol. 152. N 3. P. 1—35. (in Russian, English translation: Geol. Ore Deposites. 2024a. Vol. 66. N 8. P. 1057—1082).
  7. Bulakh M. O., Pekov I. V., Koshiyakova N. N., Nazarova M. A. Basalt alteration in high-temperature oxidizing-type fumaroles at the Tolbachik volcano (Kamchatka, Russia). Part 2. Gas metasomatites. Zapiski RMO (Proc. Russian Miner. Soc.). 2023. Vol. 152. N 5. P. 14—65. (in Russian, English translation: Geol. Ore Deposites. 2024b. Vol. 66. N 8. P. 1057—1082).
  8. Ivashchenko V. I., Golubev A. I. New aspects of mineralogy and metallogeny of the Pitkyaranta ore region. Proc. KarSC RAS. 2015. N 7. P. 127—148 (in Russian).
  9. Menyailov I. A., Nikitina L. P., Shapar V. N. Geochemical Features of Exhalations of the Great Fissure Tolbachik Eruption. Moscow: Nauka, 1980. 235 p. (in Russian).
  10. Naboko S. I. Volcanic exhalations and products of their reactions. Trudy Lab. Volcanology. 1959. Iss. 16. 300 p. (in Russian).
  11. Kravchuk T. A., Nekrasov I. Ya., Grigoriev A. P. Conditions for the formation of minerals of the ludwigite-vonsenite series according to experimental data. Zapiski VMO (Proc. Russian Miner. Soc.). 1966. Vol. 95. N 3. P. 272—286 (in Russian).
  12. Nekrasov I. Ya., Grigoriev A. P., Grigorieva T. A., Brovkin A. A., Diman E. N., Novgorodov P. G., Suknev V. S., Nikishova L. V. Study of High-Temperature Borates. Moscow: Nauka, 1970. 288 p. (in Russian).
  13. Pekov I. V., Agakhanov A. A., Zubkova N. V., Koshlyakova N. N., Shchipalkina N. V., Sandalov F. D., Yapaskurt V. O., Turchkova A. G., Sidorov E. G. Oxidizing-type fumaroles of the Tolbachik Volcano, a mineralogical and geochemical unique. Russian Geol. Geophys. 2020. Vol. 61. N 5-6. P. 675—688.
  14. Serafimova E. K. Mineralogy of Volcanic Exhalations in Kamchatka. Moscow: Nauka, 1979. 168 p. (in Russian).
  15. Shablinsky A. P., Vergasova L. P., Filatov S. K., Moskaleva S. V., Nazarova M. A., Bubnova R. S. The discovery of the mineral knasibfite K3Na4(SiF6)3(BF4) on Tolbachik volcano (Kamchatka) and details of its crystal structure. J. Volcanol. Seismol. 2020. Vol. 14. P. 177—186.
  16. Shabynin L. I. Formation of Magnesian Skarns. Moscow: Nauka, 1973. 214 p. (in Russian).
  17. Yatimov U. A., Blinov I. A., Rassomakhin M. A., Lebedeva S. M., Safaraliev N. S. Ti minerals in ores and skarns of the Aktash magnetite-polymetallic deposit, Western Karamazar, Tajikistan. Mineralogiya. 2024. Vol. 10. N 4. P. 172—185 (in Russian).
  18. Balić-Žunić T., Garavelli A., Jakobsson S. P., Jonasson K., Katerinopoulos A., Kyriakopoulos K., Acquafredda P. Fumarolic minerals: an overview of active European volcanoes. In: K. Nemeth (Ed.), Updates in Volcanology — From Volcano Modelling to Volcano Geology, 2016. P. 267—322.
  19. Bishop D. G., Wright J. D. Geology and trace elements studies of manganese occurrence in Nova Scotia. Nova Scotia Department of Mines, Econ. Geol. Series. 1974. Paper 74—1.
  20. Bollmark B. Some aspects of the origin of the Långban deposits. In: Långban: the mines their minerals, geology and explorers. Stockholm, 1999. P. 43—49.
  21. Bonin J.-O., O’Keeffe M. Takéuchitie, a new oxyborate mineral from Långban, Sweden. Amer. Miner. 1980. Vol. 65. P. 1130—1133.
  22. Boström K., Rydell H., Joensuu O. Långban — an exhalative sedimentary deposit? Econ. Geol. 1979. Vol. 74. P. 1002—1011.
  23. Burns P. C., Cooper M. A., Hawthorne F. C. Jahn-Teller-distorted Mn3+O6 octahedra in fredrikssonite, the fourth polymorph of Mg2Mn3+(BO3)O2. Canad. Miner. 1994. Vol. 32. P. 397—403.
  24. Campostrini I., Demartin F., Gramaccioli C. M., Russo M. Vulcano: The Secoli di Mineralogia. Cremona, Italy: Associazione Micro-mineralogica Italiana, 2011. 343 p.
  25. Chaplygin I. V., Yudovskaya M. A., Pekov I. V., Zubkova N. V., Britvin S. N., Vigasina M. F., Puscharovsky D. Yu., Belakovskiy D. I., Griboedova I. G., Kononkova N. N., Rassulov V. A. Marinite, IMA 2016-021. Miner. Mag. 2016. Vol. 80. P. 917.
  26. Dunn P. J., Peacor D. R., Simmons W. B., Newbury D. Fredrikssonite, a new member of pinakiolite series from Långban, Sweden. Geologiska Föreningens i Stockholm Förhandlingar. 1983. Vol. 105 (4). P. 335–340.
  27. Enholm Z. Mineral Chemistry and Paragenesis of Oxyborates in Metamorphosed Fe-Mn Oxide Deposits. Uppsala University, Sweden, 2016. 98 p.
  28. Flink G. Ueber Pinakiolith und Trimerit, zwei neue Mineralien aus den Mangangruben Schwedens. Z. Krist. 1891. Vol. 18. P. 361–376.
  29. Garavelli A., Laviano R., Varro F. Sublimate deposition from hydrothermal fluid at the Fossa crater – Vulcano, Italy. Eur. J. Miner. 1997. Vol. 9. P. 423–432.
  30. Hansen S., Hälenius U., Lindqvist B. Antimony-rich pinakiolite from Långban, Sweden: a new structural variety. Neues Jahrb. Mineral., Montash. 1988. P. 231–239.
  31. Hawthorne F. C., Burns P. C., Grice J. D. The crystal chemistry of boron. In: Boron: mineralogy, petrology and geochemistry, Reviews in Mineralogy. Mineral Society of America, 1996. Vol. 33. P. 41–115.
  32. Holstam D. Crystal chemistry of a manganian ludwigite. Neus Jahrbuch für Mineralogie – Montashiefte. 2001. N 11. P. 520–528.
  33. Huebner J. S. Stability relations of rhodochrosite in the system manganese-carbon-oxygen. Amer. Miner. 1970. Vol. 54. P. 457–481.
  34. Huebner J. S., Sato M. The oxygen fugacity-temperature relationships of manganese oxide and nickel oxide buffers. Amer. Miner. 1970. Vol. 55. P. 934–952.
  35. Koshlyakova N. N., Pekov I. V., Agakhanov A. A., Bullock E., Belakovskiy D. I., Zubkova N. V., Chukanov N. V., Britvin S. N., Bulakh M. O., Burns P. C., Hazen R. M., Zhitova E. S. Manganohatertite, IMA 2023-098. CNMNC Newsletter 77. Miner. Mag. 2024. Vol. 88. N 2. P. 203–209.
  36. Moore P. B., Araki T. Pinakiolite, Mg2Mn3+ O2[BO3]; warwickite, Mg(Mg0.5Ti0.5) O[BO3]; wightmanite, Mg5(O)(OH)5[BO3]·nH2O: crystal chemistry of complex 3 Å wallpaper structures. Amer. Miner. 1974. Vol. 59. P. 985–1004.
  37. Norrestam R., Nielsen K., Satofte I., Thorup N. Structural investigation of two synthetic oxyborates: The mixed magnesium-manganese and the pure cobalt ludwigites, Mg1.93Mn1.07O2BO3 and Co3O2BO3. Z. Krist. 1989. Vol. 189. P. 33–41.
  38. Pekov I. V., Zubkova N. V., Pautov L. A., Yapaskurt V. O., Chukanov N. V., Lykova I. S., Britvin S. N., Sidorov E. G., Pushcharovsky D. Yu. Chubarovite, KZn2(BO3)Cl2, a new mineral species from the Tolbachik volcano, Kamchatka, Russia. Canad. Miner. 2015. Vol. 53. N 2. P. 273–284.
  39. Pekov I. V., Koshlyakova N. N., Zubkova N. V., Lykova I. S., Britvin S. N., Yapaskurt V. O., Agakhanov A. A., Shchipalkina N. V., Turchkova A. G., Sidorov E. G. Fumarolic arsenates – a special type of arsenic mineralization. Eur. J. Miner. 2018. Vol. 30. N 2. P. 305–322.
  40. Pekov I. V., Zubkova N. V., Koshlyakova N. N., Belakovskiy D. I., Vigasina M. F., Britvin S. N., Sidorov E. G., Pushcharovsky D. Yu. Rhabdoborite-(V), rhabdoborite-(Mo) and rhabdoborite-(W): a new group of borate minerals with the general formula Mg12M6+1.4O6[(BO3)6-x(PO4)xF2-x] (M = V6+, Mo6+ or W6+ and x < 1). Phys. Chem. Miner. 2020. Vol. 47. N 10. Article 44.
  41. Pekov I. V., Koshlyakova N. N., Zubkova N. V., Belakovskiy D. I., Vigasina M. F., Agakhanov A. A., Ksenofontov D. A., Turchkova A. G., Britvin S. N., Sidorov E. G., Pushcharovsky D. Yu. A natural vanadate-arsenate isomorphous series with jeffbenyite-type structure: New fumarolic minerals udinaire, NaMg4(VO4)3, and arsenudinaire, NaMg4(AsO4)3. Minerals. 2022. Vol. 12. N 7. Paper 850.
  42. Randmets R. Orthopinakiolite, a new modification of Mg3Mn2+Mn23+B2O10 from Långban, Sweden. Arkiv Mineral. Geol. 1960. Vol. 2. N 42. P. 551—555.
  43. Rigaku Oxford Diffraction. CrysAlisPro Software System, v. 1.171.42.49, Rigaku Corporation, Oxford, UK. 2022.
  44. Shchipalkina N. V., Pekov I. V., Koshlyakova N. N., Britvin S. N., Zubkova N. V., Varlamov D. A., Sidorov E. G. Unusual silicate mineralization in fumarolic sublimates of the Tolbachik volcano, Kamchatka, Russia — Part 1: Neso-, cyclo-, ino- and phyllosilicates. Eur. J. Miner. 2020. Vol. 32. P. 101—119.
  45. Sheldrick G. M. Crystal structure refinement with SHELXL. Acta Cryst. 2015. Vol. C71. P. 3—8.
  46. Takeuchi Y., Haga N., Kato T., Miura Y. Orthopinakiolite, Me2.95O2[BO3]: its crystal structure and relation to pinakiolite, Me2.90O2[BO3]. Canad. Miner. 1978. Vol. 16. P. 475—485.
  47. Turchkova A. G., Pekov I. V., Yapaskurt V. O., Sidorov E. G., Britvin S. N. Manganese mineralization in fumarole deposits at the Tolbachik volcano (Kamchatka, Russia). In: IX Int. symp. “Mineral Diversity: Research and Preservation”. Sofia, 2017. P. 31—35.
  48. Zelenski M., Malik N., Taran Yu. Emissions of trace elements during the 2012—2013 effusive eruption of Tolbachik volcano, Kamchatka: enrichment factors, partition coefficients and aerosol contribution. J. Volcan. Geotherm. Research. 2014. Vol. 285. P. 136—149.

Supplementary files

Supplementary Files
Action
1. JATS XML
Download

Copyright (c) 2025 Russian Academy of Sciences