Home High-temperature Raman spectroscopy of K2Ca(CO3)2 bütschliite and Na2Ca2(CO3)3 shortite
Article
Licensed
Unlicensed Requires Authentication

High-temperature Raman spectroscopy of K2Ca(CO3)2 bütschliite and Na2Ca2(CO3)3 shortite

  • Garrett Zeff ORCID logo EMAIL logo and Quentin Williams
Published/Copyright: August 14, 2025
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 110 Issue 8

Abstract

Raman spectra of Na2Ca2(CO3)3 shortite and K2Ca(CO3)2 bütschliite were measured to 715 and 740 °C, respectively, under vacuum. The vibrational spectra demonstrate that shortite converts to nyerereite [Na2Ca(CO3)2] and calcite at 535 °C. This assemblage remains stable up to ∼700 °C, at which point nyerereite begins to decompose. Bütschliite converts to the isochemical phase fairchildite at 570 °C, which is stable to 665 °C, where it decomposes to an assemblage of K2CO3 and CaO. The variation of anharmonicity between different vibrational modes of each of the low-temperature phases is assessed, and these yield insights into inter-carbonate group couplings. Both fairchildite and nyerereite exhibit spectral features consistent with extensive disordering.

Keywords: Carbonate; high-temperature; Raman spectroscopy; carbonatite

Acknowledgments and Funding

This work was supported by the U.S. National Science Foundation through award EAR-2017294. This research was partially supported by SEES, Synchrotron Earth and Environmental Science, under NSF Cooperative Agreement EAR 2223273. We thank an anonymous reviewer and Monika Koch-Müller for helpful comments on the manuscript.

References Cited

Abersteiner, A., Golovin, A., Chayka, I., Kamenetsky, V.S., Goemann, K., Rodemann, T., and Ehrig, K. (2022) Carbon compounds in the West Kimberley lamproites (Australia): Insights from melt and fluid inclusions. Gondwana Research, 109, 536–557, https://doi.org/10.1016/j.gr.2022.06.005.Search in Google Scholar

Adler, H.H. and Kerr, P.F. (1963) Infrared spectra, symmetry and structure relations of some carbonate minerals. American Mineralogist. Journal of Earth and Planetary Materials, 48, 839–853.Search in Google Scholar

Arefiev, A.V., Shatskiy, A., Podborodnikov, I.V., Rashchenko, S.V., Chanyshev, A.D., and Litasov, K.D. (2019) The system K2CO3-CaCO3 at 3 GPa: Link between phase relations and variety of K-Ca double carbonates at ≤0.1 and 6 GPa. Physics and Chemistry of Minerals, 46, 229–244, https://doi.org/10.1007/s00269-018-1000-z.Search in Google Scholar

Balkanski, M., Wallis, R.F., and Haro, E. (1983) Anharmonic effects in light scattering due to optical phonons in silicon. Physical Review B, 28, 1928–1934, https://doi.org/10.1103/PhysRevB.28.1928.Search in Google Scholar

Ballirano, P. (2011) Thermal behaviour of natrite Na2CO3 in the 303–1013 K thermal range. Phase Transitions, 84, 357–379, https://doi.org/10.1080/01411594.2010.541856.Search in Google Scholar

Caracas, R. and Bobocioiu, E. (2011) The WURM project—A freely available web-based repository of computed physical data for minerals. American Mineralogist, 96, 437–443, https://doi.org/10.2138/am.2011.3532.Search in Google Scholar

Carper, W.R., Wahlbeck, P.G., and Griffiths, T.R. (2012) DFT models of molecular species in carbonate molten salts. The Journal of Physical Chemistry B, 116, 5559–5567, https://doi.org/10.1021/jp3016694.Search in Google Scholar

Chen, X., Wang, M., Inoue, T., Liu, Q., Zhang, L., and Bader, T. (2022) Melting of carbonated pelite at 5.5–15.5 GPa: Implications for the origin of alkali-rich carbonatites and the deep water and carbon cycles. Contributions to Mineralogy and Petrology, 177, 2.Search in Google Scholar

Cizina, M.F., Mikesell, T.D., and Kohn, M.J. (2023) Optimizing Raman spectral collection for quartz and zircon crystals for elastic thermobarometry. American Mineralogist, 108, 915–927, https://doi.org/10.2138/am-2022-8423.Search in Google Scholar

Cooper, A.F., Gittins, J., and Tuttle, O.F. (1975) The system Na2CO3-K2CO3-CaCO3 at 1 kilobar and its significance in carbonatite petrogenesis. American Journal of Science, 275, 534–560, https://doi.org/10.2475/ajs.275.5.534.Search in Google Scholar

Dickens, B., Hyman, A., and Brown, W.E. (1971) Crystal structure of Ca2Na2(CO3)3 (shortite). Journal of Research of the National Bureau of Standards – A, Physics and Chemistry, 75A, 129–135, https://doi.org/10.6028/jres.075A.013.Search in Google Scholar

Estep, P.A., Kovach, J.J., Hiser, A.L., and Karr, C. (1970) Characterization of carbonate minerals in oil shales and coals by infrared spectroscopy. In R.A. Friedel, Ed., Spectrometry of Fuels, p. 228–247. Springer.Search in Google Scholar

Farsang, S., Facq, S., and Redfern, S. (2018) Raman modes of carbonate minerals as pressure and temperature gauges up to 6 GPa and 500 °C. American Mineralogist, 103, 1988–1998.Search in Google Scholar

Fontana, M.D., Brehat, F., and Wyncke, B. (1990) A central peaks as a pre-melting feature in NaNO3 spectra. Journal of Physics: Condensed Matter, 2, 9125–9131, https://doi.org/10.1088/0953-8984/2/46/012.Search in Google Scholar

Frost, R.L. and Dickfos, M.J. (2008) Raman and infrared spectroscopic study of the anhydrous carbonate minerals shortite and barytocalcite. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 71, 143–146, https://doi.org/10.1016/j.saa.2007.11.021.Search in Google Scholar

Gervasoni, F., Klemme, S., Rohrbach, A., Grützner, T., and Berndt, J. (2017) Experimental constraints on mantle metasomatism caused by silicate and carbonate melts. Lithos, 282-283, 173–186, https://doi.org/10.1016/j.lithos.2017.03.004.Search in Google Scholar

Gillet, P., Biellmann, C., Reynard, B., and McMillan, P. (1993) Raman spectroscopic studies of carbonates part I: High-pressure and high-temperature behaviour of calcite, magnesite, dolomite and aragonite. Physics and Chemistry of Minerals, 20, 1–18, https://doi.org/10.1007/BF00202245.Search in Google Scholar

Johnson, D., Smith, J.W., and Robb, W.A. (1974) Thermal characteristics of shortite, Volume 7862, U.S. Department of the Interior, Bureau of Mines.Search in Google Scholar

Kamenetsky, V.S. and Yaxley, G.M. (2015) Carbonate–silicate liquid immiscibility in the mantle propels kimberlite magma ascent. Geochimica et Cosmochimica Acta, 158, 48–56, https://doi.org/10.1016/j.gca.2015.03.004.Search in Google Scholar

Likhacheva, A.Y., Miloš, S., Romanenko, A.V., Goryainov, S.V., Semerikova, A.I., Rashchenko, S.V., Miletich, R., and Shatsky, A. (2024a) High-pressure behavior and stability of synthetic buetschliite K2Ca(CO3)2 up to 19 GPa and 300 °C. Journal of Raman Spectroscopy, 55, 517–524, https://doi.org/10.1002/jrs.6654.Search in Google Scholar

Likhacheva, A. Yu., Romanenko, A.V., Rashchenko, S.V., Miloš, S., Lotti, P., Miletich, R., and Shatskiy, A. (2024b) Crystallographic mechanism of the elastic behaviour of synthetic bütschliite K2Ca(CO3)2 on compression to 20 GPa. Physics and Chemistry of Minerals, 51, 29, https://doi.org/10.1007/s00269-024-01291-8.Search in Google Scholar

Logvinova, A.M., Shatskiy, A., Wirth, R., Tomilenko, A.A., Ugap’eva, S.S., and Sobolev, N.V. (2019) Carbonatite melt in type Ia gem diamond. Lithos, 342-343, 463–467, https://doi.org/10.1016/j.lithos.2019.06.010.Search in Google Scholar

Lucazeau, G. (2003) Effect of pressure and temperature on Raman spectra of solids: Anharmonicity. Journal of Raman Spectroscopy, 34, 478–496, https://doi.org/10.1002/jrs.1027.Search in Google Scholar

Luty, T. and Eckhardt, C.J. (1985) Piezomodulated Raman spectroscopy of molecular crystals: An experimental method for study of the anharmonic properties of solids. The Journal of Chemical Physics, 82, 1515–1521, https://doi.org/10.1063/1.448426.Search in Google Scholar

Mernagh, T.P., Kamenetsky, V.S., and Kamenetsky, M.B. (2011) A Raman micro-probe study of melt inclusions in kimberlites from Siberia, Canada, SW Greenland and South Africa. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 80, 82–87, https://doi.org/10.1016/j.saa.2011.01.034.Search in Google Scholar

Navrotsky, A., Putnam, R.L., Winbo, C., and Rosen, E. (1997) Thermochemistry of double carbonates in the K2CO3-CaCO3 system. American Mineralogist, 82, 546–548, https://doi.org/10.2138/am-1997-5-614.Search in Google Scholar

Neumann, G. and Vogt, H. (1978) Rayleigh wing scattering in disordered sodium nitrate. Physica Status Solidi B: Basic Research, 85, 179–184, https://doi.org/10.1002/pssb.2220850119.Search in Google Scholar

Pabst, A. (1974) Synthesis, properties, and structure of K2Ca(CO3)2, buetschliite. American Mineralogist, 59, 6.Search in Google Scholar

Pal’yanov, N., Sokol, A.G., Borzdov, M., and Khokhryakov, A.F. (2002) Fluid-bearing alkaline carbonate melts as the medium for the formation of diamonds in the Earth’s mantle: An experimental study. Lithos, 60, 145–159, https://doi.org/10.1016/S0024-4937(01)00079-2.Search in Google Scholar

Peercy, P.S. (1973) Uniaxial-stress dependence of the Raman-active phonons in TiO2. Physical Review B, 8, 6018–6020, https://doi.org/10.1103/PhysRevB.8.6018.Search in Google Scholar

Pertlik, F., Ed. (1981) Structural investigations of synthetic fairchildite, K2Ca(CO3)2. Zeitschrift für Kristallographie. Crystalline Materials, 157, 199–205, https://doi.org/10.1524/zkri.1981.157.3-4.199.Search in Google Scholar

Podborodnikov, I.V., Shatskiy, A., Arefiev, A.V., Rashchenko, S.V., Chanyshev, A.D., and Litasov, K.D. (2018) The system Na2CO3-CaCO3 at 3 GPa. Physics and Chemistry of Minerals, 45, 773–787, https://doi.org/10.1007/s00269-018-0961-2.Search in Google Scholar

Reeder, R. and Markgraf, S. (1986) High-temperature crystal chemistry of dolomite. American Mineralogist, 71, 795–804.Search in Google Scholar

Shatskiy, A., Sharygin, I.S., Litasov, K.D., Borzdov, Y.M., Palyanov, Y.N., and Ohtani, E. (2013) New experimental data on phase relations for the system Na2CO3-CaCO3 at 6 GPa and 900–1400 °C. American Mineralogist, 98, 2164–2171, https://doi.org/10.2138/am.2013.4436.Search in Google Scholar

Shen, T.Y., Mitra, S.S., Prask, H., and Trevino, S.F. (1975) Order-disorder phenomenon in sodium nitrate studied by low-frequency Raman scattering. Physical Review B, 12, 4530–4533, https://doi.org/10.1103/PhysRevB.12.4530.Search in Google Scholar

Vennari, C.E., Beavers, C.M., and Williams, Q. (2018) High-pressure/temperature behavior of the alkali/calcium carbonate shortite (Na2Ca2(CO3)3) Implications for carbon sequestration in Earth’s transition zone. Journal of Geophysical Research: Solid Earth, 123, 6574–6591, https://doi.org/10.1029/2018JB015846.Search in Google Scholar

Wang, X., Ye, Y., Wu, X., Smyth, J.R., Yang, Y., Zhang, Z., and Wang, Z. (2019) High-temperature Raman and FTIR study of aragonite-group carbonates. Physics and Chemistry of Minerals, 46, 51–62, https://doi.org/10.1007/s00269-018-0986-6.Search in Google Scholar

Weiss, Y., McNeill, J., Pearson, D.G., Nowell, G.M., and Ottley, C.J. (2015) Highly saline fluids from a subducting slab as the source for fluid-rich diamonds. Nature, 524, 339–342, https://doi.org/10.1038/nature14857.Search in Google Scholar

Winbo, C., Rosen, E., Heim, M., Garcia, F., Barré, L., Hammerich, O., Søtofte, I., and Långström, B. (1998) Thermal analytical study of the decomposition of K2Ca(CO3)2. Acta Chemica Scandinavica, 52, 431–434, https://doi.org/10.3891/acta.chem.scand.52-0431.Search in Google Scholar

Ye, Y., Smyth, J.R., and Boni, P. (2012) Crystal structure and thermal expansion of aragonite-group carbonates by single-crystal X-ray diffraction. American Mineralogist, 97, 707–712, https://doi.org/10.2138/am.2012.3923.Search in Google Scholar

Zaitsev, A.N. and Chakhmouradian, A.R. (2002) Calcite amphibole clinopyroxene rock from the Afrikanda Complex, Kola Peninsula, Russia: Mineralogy and a possible link to carbonatites. II. Oxysalt minerals. Canadian Mineralogist, 40, 103–120, https://doi.org/10.2113/gscanmin.40.1.103.Search in Google Scholar

Zaitsev, A.N., Keller, J., Spratt, J., Jeffries, T.E., and Sharygin, V.V. (2009) Chemical composition of nyerereite and gregoryite fromnatrocarbonatites of Oldo inyo Lengai volcano, Tanzania. Geology of Ore Deposits, 51, 608–616, https://doi.org/10.1134/S1075701509070095.Search in Google Scholar

Zeff, G., Kalkan, B., Armstrong, K., Kunz, M., and Williams, Q. (2024) High pressure Raman spectroscopy and X-ray diffraction of K2Ca(CO3)2 bütschliite: Multiple pressure-induced phase transitions in a double carbonate. Physics and Chemistry of Minerals, 51, 2, https://doi.org/10.1007/s00269-023-01262-5.Search in Google Scholar

Zhao, Z., Wang, D., Wang, Q., Li, Z., and Fang, Z. (2013) Quantum chemical study on thermal decomposition mechanism of calcium carbonate. Journal of Theoretical and Computational Chemistry, 12, 1350049, https://doi.org/10.1142/S0219633613500491.Search in Google Scholar

Zhao, Z., Li, Z., Wang, Q., and Wang, Y. (2015) Quantum chemical study of thermal decomposition mechanism and polymorph predict phase transitions of magnesite. Research on Chemical Intermediates, 41, 8471–8482, https://doi.org/10.1007/s11164-014-1904-2.Search in Google Scholar
Received: 2024-06-16
Accepted: 2024-11-27
Published Online: 2025-08-14
Published in Print: 2025-08-26

© 2025 Mineralogical Society of America

Articles in the same Issue

  1. Hematite (U-Th)/He thermochronometry unveils unique exhumation history: An example from the Dexing porphyry copper deposit, Southern China
  2. Viscosity measurements of selected lunar regolith simulants
  3. Formation of nano-CdS solid solution: A mechanism for Cd enrichment in sphalerite
  4. Identification of the nature of recycled carbonates in the mantle: Insights from the Mo-Mg isotopic pair
  5. Discriminating ionic mobility between diffusivity and electrical conductivity experiments on Earth’s silicate materials
  6. Morphological approach to understanding mineral alteration and nanoparticle formation under alkaline conditions using granitic rock thin sections
  7. Identification of hydroandradite in CM carbonaceous chondrites: Aproduct of calc-silicate alteration on C-complex asteroids
  8. Growth and crystallographic features of interpenetrant twins in natural diamonds
  9. Determination of the oxidation state of iron in calcic pyroxene using the electron microprobe flank method
  10. Formation mechanism of boehmite and diaspore in karstic bauxites: Trace element geochemistry in source materials using a large sample geochemical dataset and a random forest model
  11. High-temperature Raman spectroscopy of K2Ca(CO3)2 bütschliite and Na2Ca2(CO3)3 shortite
  12. Effects of high-temperature annealing and low-temperature metamictization on Archean zircon: Constraints from U-Pb isotopes, trace elements, and Raman dating
  13. Nanoscale insights into weathering of Ti-bearing minerals and heterogeneous crystal growth mechanisms of nano Ti oxides in altered volcanic ash
  14. High-pressure single-crystal X-ray diffraction and Raman spectroscopy of boltwoodite, K0.63Na0.37[(UO2)(SiO3OH)](H2O)1.5
  15. Nanoscale characterization of chrysocolla, black chrysocolla, and pseudomalachite from supergene copper deposits of Atacama Desert in northern Chile
https://doi.org/10.2138/am-2024-9500
Keywords for this article
Carbonate; high-temperature; Raman spectroscopy; carbonatite

Articles in the same Issue

  1. Hematite (U-Th)/He thermochronometry unveils unique exhumation history: An example from the Dexing porphyry copper deposit, Southern China
  2. Viscosity measurements of selected lunar regolith simulants
  3. Formation of nano-CdS solid solution: A mechanism for Cd enrichment in sphalerite
  4. Identification of the nature of recycled carbonates in the mantle: Insights from the Mo-Mg isotopic pair
  5. Discriminating ionic mobility between diffusivity and electrical conductivity experiments on Earth’s silicate materials
  6. Morphological approach to understanding mineral alteration and nanoparticle formation under alkaline conditions using granitic rock thin sections
  7. Identification of hydroandradite in CM carbonaceous chondrites: Aproduct of calc-silicate alteration on C-complex asteroids
  8. Growth and crystallographic features of interpenetrant twins in natural diamonds
  9. Determination of the oxidation state of iron in calcic pyroxene using the electron microprobe flank method
  10. Formation mechanism of boehmite and diaspore in karstic bauxites: Trace element geochemistry in source materials using a large sample geochemical dataset and a random forest model
  11. High-temperature Raman spectroscopy of K2Ca(CO3)2 bütschliite and Na2Ca2(CO3)3 shortite
  12. Effects of high-temperature annealing and low-temperature metamictization on Archean zircon: Constraints from U-Pb isotopes, trace elements, and Raman dating
  13. Nanoscale insights into weathering of Ti-bearing minerals and heterogeneous crystal growth mechanisms of nano Ti oxides in altered volcanic ash
  14. High-pressure single-crystal X-ray diffraction and Raman spectroscopy of boltwoodite, K0.63Na0.37[(UO2)(SiO3OH)](H2O)1.5
  15. Nanoscale characterization of chrysocolla, black chrysocolla, and pseudomalachite from supergene copper deposits of Atacama Desert in northern Chile
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 25.10.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2024-9500/html
Scroll to top button