Transformation series parakeldyshite-keldyshite: mechanism of transformation, chemical formula revision and crystal structure of keldyshite

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Abstract

A holotype sample of keldyshite has been studied and found to consist of aggregates of partially protonated, Na-deficient parakeldyshite (which is predominant) and keldyshite itself. A series of laboratory experiments on the hydrolysis of parakeldyshite was conducted, leading to the clarification of the crystal structure of keldyshite formed during this process. An idealized refined formula for keldyshite, (Na□)ZrSi2O6(OH), has been obtained. As a result of the protonation of the oxygen atom at position O5 and the formation of strong hydrogen bonds (with an O5...O5 distance of 2.458 Å in keldyshite), a series of hinge transformations occurs, causing significant distortion of the Zr–Si–O framework within the crystal structure. The existence of the transformation series from parakeldyshite to keldyshite in nature has been confirmed. The mechanism for keldyshite formation can be described by the reaction scheme: Na+ + O2‒ → □ + (OH)‒. It is likely that the substitution reaction of parakeldyshite by keldyshite occurs via a transition from single crystal to single crystal.

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About the authors

T. L. Panikorovskii

Kola Scienсe Centre of the Russian Academy of Sciences

Author for correspondence.
Email: t.panikorovskii@ksc.ru
Russian Federation, Apatity

G. O. Samburov

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Russian Federation, Apatity

A. P. Nikolaev

Apatite Museum and Exhibition Centre

Email: t.panikorovskii@ksc.ru
Russian Federation, Kirovsk

A. V. Bazai

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Russian Federation, Apatity

O. F. Goychuk

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Russian Federation, Apatity

I. V. Pekov

Moscow State University

Email: t.panikorovskii@ksc.ru
Russian Federation, Moscow

S. V. Krivovichev

Kola Scienсe Centre of the Russian Academy of Sciences; St. Petersburg State University

Email: t.panikorovskii@ksc.ru
Russian Federation, Apatity; St. Petersburg

References

  1. Герасимовский В.И. // Докл. АН СССР. 1962. Т. 142. № 4. С. 916.
  2. Хомяков А.П., Казакова М.Е., Воронков А.А. // Докл. АН СССР. 1969. Т. 189. № 1. С. 166.
  3. Хомяков А.П., Воронков А.А., Казакова М.Е. и др. // Тр. Минерал. музея АН СССР. 1975. Т. 24. С. 120.
  4. Хомяков А.П. Геохимия. Минералогия: Междунар. геол. конгр. XXV сес.: Докл. сов. геологов. Москва, 1976. С. 233.
  5. Хомяков А.П. // Докл. АН СССР. 1977. Т. 237. № 3. С. 703.
  6. Хомяков А.П. // Природа. 2011. № 12. С. 35.
  7. Воронков А.А., Шумяцкая Н.Г., Пятенко Ю.А. // Журн. структур. химии. 1970. Т. 11. № 5. С. 932.
  8. Сизова Р.Г. Воронков А.А., Хомяков А.П. // Структура и свойства кристаллов. Владимир: ВГПИ, 1974. № 2. С. 30.
  9. Халилов А.Д., Хомяков А.П., Махмудов С.А. // Докл. АН СССР. 1978. Т. 238. № 3. С. 573.
  10. Хомяков А.П. Минералогия ультраагпаитовых щелочных пород. М.: Наука, 1990. 200 с.
  11. Хомяков А.П. // Научные основы и практическое использование типоморфизма минералов. М.: Наука, 1980. С. 152.
  12. Хомяков А.П., Юшкин Н.П. // Докл. АН СССР. 1981. Т. 256. № 5. С. 1229.
  13. Хомяков А.П. // Развитие минералогии и геохимии и их связь с учением о полезных ископаемых. М.: Наука, 1983. С. 66.
  14. Юшкин Н.П., Хомяков А.П., Евзикова Н.З. Принцип наследования в минералогенезисе. Сыктывкар: Коми научный центр, 1984. 32 с.
  15. Khomyakov A.P. 30th Int. Geol. Congress. Beijing, 1996. V. 2/3. P. 450.
  16. Челищев Н.Ф., Хомяков А.П., Беренштейн Б.Г. и др. // А.с. 1096794 (СССР). Способ очистки газов от двуокиси серы / ИМГРЭ–ВАМИ. Б.И. 1984. № 21.
  17. Илюшин Г.Д., Демьянец Л.Н. // Кристаллография. 1988. Т. 33. С. 650.
  18. Зубкова Н.В., Пеков И.В., Турчкова А.Г. и др. // Кристаллография. 2007. Т. 52. № 1. С. 68.
  19. Zubkova N.V., Ksenofontov D.A., Chukanov N.V. et al. // Minerals. 2020. V. 10. № 3. P. 243. https://doi.org/10.3390/min10030243
  20. Zubkova N.V., Nikolova R.P., Chukanov N.V. et al. // Minerals. 2019. V. 9. № 7. P. 420. https://doi.org/10.3390/min9070420
  21. Чуканов Н.В., Пеков И.В., Расцветаева Р.К. // Успехи химии. 2004. Т. 73. Вып. 3. С. 227. https://doi.org/10.1070/RC2004v073n03ABEH000825
  22. Chukanov N.V., Pekov I.V. // Rev. Mineral. Geochem. 2005. V 57. P. 105. https://doi.org/10.2138/rmg.2005.57.4
  23. Pekov I.V., Chukanov N.V. // Rev. Mineral. Geochem. 2005. V. 57. P. 145. https://doi.org/10.2138/rmg.2005.57.5
  24. Пеков И.В., Зубкова Н.В., Пущаровский Д.Ю. и др. // Кристаллография. 2007. Т. 52. № 6. С. 1100.
  25. Nikolova R.P., Fujiwara K., Nakayama N., Kostov-Kytin V. // Solid State Sci. 2009. V. 11. № 2. P. 382. https://doi.org/10.1016/j.solidstatesciences.2008.07.003
  26. Kabanova N.A., Panikorovskii T.L., Shiloskikh V.V. et al. // Crystals. 2020. V. 10. № 11. P. 1016. https://doi.org/10.3390/cryst10111016
  27. Agilent Technologies CrysAlis CCD and CrysAlis RED. Oxford Diffr. Ltd, Yarnton, Oxfordsh. 2014.
  28. Sheldrick G.M. // Acta Cryst. C. 2015. V. 71. P. 3. https://doi.org/10.1107/S2053229614024218
  29. Brese N.E., O'Keeffe M. // Acta Cryst. B. 1991. V. 47. P. 192. https://doi.org/10.1107/S0108768190011041
  30. Dolivo-Dobrovolsky D.D. MINAL. http://www.dimadd.ru. Accessed 15 May 2016.
  31. McCusker L.B., Liebau F., Engelhardt G. // Micropor. Mesopor. Mater. 2003. V. 58. P. 3.
  32. Jeffrey G.A. An Introduction to Hydrogen Bonding, Oxford: Oxford University Press, 1997.

Supplementary files

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2. Fig. 1. Sample No. 9518: parakeldyshite (1) and snow-white pseudomorph of keldyshite (2) after it in association with aegirine (3), eudialyte (4), nepheline (5) and murmanite (6). Umbozero mine, Alluaiv town, Lovozero.

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3. Fig. 2. SEM images of samples MVC No. 465 (a, b, d) and No. 9518 (c), obtained in the backscattered electron detection mode: parakeldyshite (1), keldyshite (2), phase M-34 (3), catapleite (4), hydroxynatropyrochlore (5).

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4. Fig. 3. X-ray phase analysis of the initial parakeldyshite (1) and phases after treatment for seven days with an acid solution at 20 (2) and 70°C (3). The calculated diffraction pattern of the M-34 phase (4), experimental diffraction patterns of keldyshite (01-072-1944) (5) and parakeldyshite (00-029-1293) (6) are shown.

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5. Fig. 4. Projections of the crystal structures on the (100) plane of the original parakeldyshite No. 9518 (a), parakeldyshite MVC No. 465 (b), keldyshite obtained during the hydrolysis of sample No. 9518 (c), and keldyshite (d) described in [9].

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6. Fig. 5. Projections of the zirconium silicate framework of parakeldyshite MVC No. 465 on the planes (100) (a) and (010) (b); similar projections of keldyshite obtained during hydrolysis of sample No. 9518 (c, d).

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7. Fig. 6. Bond lengths in the coordination polyhedra of Zr, Na1 and Na2 (a–c) in the structures of parakeldyshite MVC No. 465 and keldyshite obtained during hydrolysis of sample No. 9518 (d–e).

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8. Fig. 7. Fragments of the crystal structures of parakeldyshite MVC No. 465 (a) and keldyshite obtained during hydrolysis of sample No. 9518 (b). The arrows indicate the formation of a hydrogen bond between the O5…O5 atoms.

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