Crystal structure and raman spectroscopy of synthetic potassium Richterite

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Abstract

The structures of two potassium richterite crystals with crystal chemical formulas (K0.44Na0.32□0.24)Σ=1(Ca1.18Na0.82) were studied by single-crystal X-ray diffraction analysis and Raman spectroscopy (RAMAN)Σ=2Mg5Si8O22OH2 and (K0.83Na0.02□0.15)Σ=1(Ca1.18Na0.89)Σ=2Mg5Si8O22OH2 synthesized at a pressure of 3 GPa and a temperature of 1000°C in the MgSiO3+CaMgSi2O6+K2CO3+Na2CO3+CO2+ +H2O system. The parameters of monoclinic cells are obtained: a=10.0256(5) & 9.9748(11), b=17.9874(7) & 17.9879(16), c=5.2687(3) & 5.2746(6) Å, Vu.c. = 916.17(18) & 918.52(8) Å3, β = 104.520(12)o & 104.821(5)o, sp. gr. С2/m (12), Z = 2. It was found that positions M(1), M(2) and M(3) are inhabited by Mg2+, position M(4) is occupied simultaneously by Ca2+ and Na+. The Na+ cations that are not included in M(4) are located in position A, which also accommodates K+ cations. Raman spectroscopy showed the presence of vacancies in position A in both samples. The structure corresponds to the “ideal” structure of richterite group minerals. The unit cell volumes of the measured crystals are directly proportional to the content of K in position A. Based on the generalization of new and published data, an equation of dependence of Vu.c. fоr amphiboles of the richterite Na(NaCa)Mg5Si8O22(OH)2–K-richterite K(NaCa)Mg5Si8O22(OH)2 series with a low tremolite component on the K content in position A is proposed.

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About the authors

E. V. Limanov

D.S. Korzhinsky Institute of Experimental Mineralogy, Russian Academy of Sciences

Author for correspondence.
Email: spivak@iem.ac.ru
Russian Federation, Chernogolovka

V. G. Butvina

D.S. Korzhinsky Institute of Experimental Mineralogy, Russian Academy of Sciences

Email: spivak@iem.ac.ru
Russian Federation, Chernogolovka

O. G. Safonov

D.S. Korzhinsky Institute of Experimental Mineralogy, Russian Academy of Sciences; M.V. Lomonosov Moscow State University

Email: spivak@iem.ac.ru
Russian Federation, Chernogolovka; Moscow

A. V. Spivak

D.S. Korzhinsky Institute of Experimental Mineralogy, Russian Academy of Sciences

Email: spivak@iem.ac.ru
Russian Federation, Chernogolovka

A. V. Kuzmin

D.S. Korzhinsky Institute of Experimental Mineralogy, Russian Academy of Sciences; Yu.A. Osipyan Institute of Solid State Physics, Russian Academy of Sciences

Email: spivak@iem.ac.ru

аcademician of the RAS

Russian Federation, Chernogolovka; Chernogolovka

L. Ya. Aranovich

D.S. Korzhinsky Institute of Experimental Mineralogy, Russian Academy of Sciences; Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry of the Russian Academy of Sciences

Email: spivak@iem.ac.ru
Russian Federation, Chernogolovka; Moscow

References

  1. Hawthorne F.C., Oberti R., Harlow G.E., Maresch W.V., Martin R.F., Schumacher J.C., Welch M.D. Nomenclature of the amphibole supergroup // Am. Mineral. 2012. V. 97. P. 2031–2048.
  2. Gottschalk M., Andrut M. Structural and chemical characterization of synthetic (Na,K)-richterite solid solutions by EMP, HRTEM, XRD and OH-valence vibrational spectroscopy // Phys Chem Minerals. 1998. V. 25. P. 101–111.
  3. Huebner J.H., Papike J.J. Synthesis and crystal chemistry of sodium-potassium richterite, (Na,K)NaCaMg5,Si8O22(OH,F)2: a model for amphiboles // Am. Mineral. 1970. V. 55. P. 1973–1992.
  4. Dawson J.B., Smith J.V. The MARID (mica-amphibole-rutile-ilmenite-diopside) suite of xenoliths in kimberlite // Geochimica et Cosmochimica Acta. 1977. V. 41. P. 309–323.
  5. Foley S. High-pressure stability of the fluor- and hydroxyendmembers of pargasite and K-richterite // Geochim Cosmochim Acta. 1991. V. 55. P. 2689–2694.
  6. Сафонов О.Г., Бутвина В.Г. Реакции – индикаторы активности K и Na в верхней мантии: природные и экспериментальные данные, термодинамическое моделирование // Геохимия. 2016. № 3. С. 893–908.
  7. Limanov. E.V., Butvina V.G., Safonov O. G., Spivak A. V., Van K. V., Vorobey S. S. Formation of Richterite in the Enstatite-Diopside System in the Presence of K2CO3-Na2CO3-CO2-H2O Fluid: Implications for the Processes of Mantle Metasomatism // Geochem. Int. 2024. V. 62. № 4. P. 356–365.
  8. Konzett J., Ulmer P. The stability of hydrous potassic phases in lherzolitic mantle – an experimental study to 9.5 GPa in simplified and natural bulk compositions // J. Petrol. 1999. V 40. № 4. P. 629–652.
  9. Zimmermann R., Gottschalk M., Heinrich W., Franz G. Experimental Na-K distribution between amphiboles and aqueous chloride solutions, and a mixing model along the richterite-K-richterite join // Contrib. Mineral. Petrol. 1997. V. 126. №3. P. 252–264.
  10. Aoki K. Origin of phlogopite and potassic richterite bearing peridotite xenoliths from South Africa // Contrib. to Mineral. Petrol. 1975. V. 53 №3. P. 145–156.
  11. Yang H., Konzett J., Prewitt C.T., Fei Y. Single-crystal structure refinement of synthetic M4K-substituted potassic-richterite, K(KCa)Mg5Si8O22(OH)2 // Am. Mineral. 1999. 84:681–684
  12. CrysAlisPro: 1.171.41.118a. (Rigaku Oxford Diffraction, 2019). CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27.03.2014 CrysAlis171. NET).
  13. Sheldrick G.M. SHELX97: Program for the solution and refinement of crysta structures. University of Göttingen, Germany, 1997.
  14. Della Ventura G., Hawthorne F.C., Mihailova B., Sodo A. Raman and FTIR Spectroscopy of Synthetic Amphiboles: I. The OH Librational Bands and the Determination of the OH-F Content of Richterites via Raman Spectroscopy // Can. Mineral. 2021. V. 59. №1. P. 31–41.
  15. Hawthorne F.C., Della Ventura G. Short-range order in amphiboles / In: Hawthorne FC, Oberti R, Della Ventura G, Mottana A (eds) Amphiboles: crystal chemistry, occurrence and health issues // Reviews in Mineralogy. 2007. V. 67. P. 173–222.
  16. Robert J.L., Della Ventura G., Thauvin J.L. The infrared OH-streching region of synthetic richterites in the system Na2O-K2O-CaO-MgO-SiO2-H2O-HF // Eur. J. Mineral. 1989. V. 1. P. 203–211.
  17. Dumanska-Słowik M., Powolny T., Natkaniec-Nowak L., Stankiewicz K. Mineralogical and geochemical implications on the origin of dianite from the alkaline Murun Complex (Eastern Siberia, Russia) // Ore Geol. Rev. 2022. V. 141. P. 1–13.
  18. Raudsepp M., Della Ventura G., Hawthorne F.C. Data for Synthetic Potassium-Richterite, Nickel-Potassium, Richterite and Cobalt-Potassium-Richterite // Powder Diffraction. 1992. V.7. № 1. P. 52–55.
  19. Hawthorne F.C., Ventura G.D., Robert J.L., Welch M.D., Raudsepp M., Jenkins D.M. A Rietveld and infrared study of synthetic amphiboles along the potassium-richterite–tremolite join // Am. Mineral. 1997. V. 82. № 7–8. P. 708–716.
  20. Pawley A.R., Graham C.M., Navrotsky A. Tremolite-richterite amphiboles: synthesis, compositional and structural characterization, and thermochemistry // Am. Mineral. 1993. V. 78. P. 20–26.

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2. Fig. 1. SEM photographs of K-richterite crystals from the products of experiments II-40 and III-60 in the system MgSiO3+CaMgSi2O6+ +K2CO3+Na2CO3+CO2+H2O [7].

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3. Fig. 2. Crystal structure of synthetic potassium richterite (this work).

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4. Fig. 3. Raman spectra in the range of 100–4000 cm–1 of synthetic K-richterites, processed using the Fityk 1.3.1 and Origin2021 software packages.

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5. Fig. 4. Dependences of the V e. y. of amphiboles of the richterite–K-richterite series on the K content in position A. Data points: orange [2, 9], green [3], black [18, 19], large red – this work. Dashed lines – approximations presented by equations (2–4), see text.

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