Geosciences Journal

, Volume 22, Issue 2, pp 303–312 | Cite as

Determination and estimation of magnesium content in the single phase magnesium-calcite [Ca(1−x)MgxCO3(s)] using electron probe micro-analysis (EPMA) and X-ray diffraction (XRD)

  • Muhammad Fahad
  • Sundas Saeed


Mg-calcite (MgCc) is the term used for calcite containing variable magnesium content. The correct determination of the Mg-content in the calcite is of great interest for many fields of research. This study presents the potential, accuracy and the limitations of determining Mg-content in MgCc by means of electron probe micro-analysis (EPMA) coupled with the energy dispersive and wave dispersive spectrometry (EDS/WDS), and X-ray diffractometry (XRD). These techniques were used to examine the distribution of Mg (in mol% MgCO3) in six calcite marble samples from different locations of Peshawar basin (Pakistan), a part of Lesser Himalayas. Results showed variable Mg-content averaging 0.944–1.740 mol% from the chemical analysis with EPMA/EDS of the whole rock sample. This was almost consistent with the XRD findings of 0.750–1.690 mol%. The sample NO13 with heteroblastic grain structure showed disequilibrium geometry due to the contact metamorphism, characterized by the relatively high temperature and low pressure. This caused predominantly quick re-crystallization of the carbonate phase, thus showing lower Mg-content in the sample. It was assumed that the observed small variability in the Mg-content of the investigated calcites even with in the sample is due to the temperature dependency of the Mg incorporation into the calcites. The highest degree of accuracy in Mg-content determination was observed based on the lattice parameter a and cell volume V. For the Mg-content obtained by XRD, best correlation was observed between the lattice parameter a, cell volume V and Mg-content, with r2 = 0.991 and 0.990 respectively. The difference between the d104 values from the Rietveld refinement and the observed XRD patterns were generally < 0.002 Å.

Key words

magnesium calcite electron microprobe XRD calcite Rietveld refinement 


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  1. Baitalow, F., Wolf, G., and Schmidt, H.G., 1998, Thermochemical investigations of calcium carbonate phase transitions 1. Thermal activated vaterite-calcite transition. Journal of Thermal Analysis and Calorimetry, 52, 5–16.CrossRefGoogle Scholar
  2. Bertram, M.A., Mankenzie, F.T., Bischoff, F.C., and Bischoff, W.D., 1991, Influence of temperature on the stability of magnesian calcite. American Mineralogist, 76, 1889–1896.Google Scholar
  3. Bragg, W.L., 1914a, The structure of some crystals as indicated by their diffraction of X-rays. Proceedings of the Royal Society of London, 89, 248–277.CrossRefGoogle Scholar
  4. Bragg, W.L., 1914b, The analysis of crystals by the X-ray spectrometer. Proceedings of the Royal Society of London, 89, 468–489.CrossRefGoogle Scholar
  5. Busenberg, E. and Plummer, L.N., 1989, Thermodynamics of magnesium calcite solid-solution at 25 °C and 1 atm total pressure. Geochimica et Cosmochimica Acta, 53, 1189–1208.CrossRefGoogle Scholar
  6. Bischoff, W.D., Bishop, F.C., and Mackenzie, F.T., 1983, Biogenically produced magnesium calcite: inhomogeneities in chemical and physical properties; comparison with synthetic phases. American Mineralogist, 68, 1183–1188.Google Scholar
  7. Chessin, H., Hamilton, W.C., and Post, B., 1965, Position and thermal parameters of oxygen atom in calcite. Acta Crystallographica, 18, 689–693.CrossRefGoogle Scholar
  8. Chave, K.E., 1952, A solid solution between calcite and dolomite. Journal of Geology, 60, 190–192.CrossRefGoogle Scholar
  9. Chave, K.E., 1954, Aspects of the biogeochemistry of magnesium 1. Calcareous marine organisms. Journal of Geology, 62, 266–283.CrossRefGoogle Scholar
  10. Chave, K.E., Deffeyes, K.S., Weyl, P.K., Garrel, R.M., and Thompson, M.E., 1962, Observations on the solubility of skeletal carbonates in aqueous solutions. Science, 137, 33–34.CrossRefGoogle Scholar
  11. Cheary, R.W. and Coelho, A.A., 1992, A fundamental parameter approach to X-ray line-profile fitting. Journal of Applied Crystallography, 25, 109–121.CrossRefGoogle Scholar
  12. Cheary, R.W., Coelho, A.A., and Cline, J.P., 2004, Fundamental parameters line profile fitting in laboratory diffractometers. Journal of Research of the National Institute of Standards and Technology, 109, 1–25.CrossRefGoogle Scholar
  13. De-Villier, S., Greaves, M., and Elderfield, H., 2002, An intensity ratio calculation method for the accurate determination of Mg/Ca and Sr/Ca of marine carbonates by ICP-AES. Geochemistry, Geophysics, Geosystems, 3, 2001G000169.Google Scholar
  14. Erenburg, B.C., 1961, Artificial mixed carbonates in the CaCO3-MgCO3 series. Zhurnal Strukturnoi Khimii, 2, 178–182.Google Scholar
  15. Fahad, M., Iqbal, Y., Riaz, M., Ubic, R., and Redfern, S.A.T., 2016, Metamorphic temperature investigation of coexisting Calcite and dolomite marbles–examples from Nikani Ghar marble and Nowshera Formation, Peshawar Basin, Pakistan. Journal of Earth Sciences, 27, 989–997.Google Scholar
  16. Falini, G., Gazzano, M., and Ripamonti, A., 1996, Magnesium calcite crystallization from water-alcohol mixtures. Chemical Communications, 271, 1037–1038.CrossRefGoogle Scholar
  17. Franzini, M., Lezzerini, M., and Origlia, F., 2010, Marbles from the Campiglia Marittima area (Tuscany, Italy) used in the antiquity. European Journal of Mineralogy, 22, 881–893.CrossRefGoogle Scholar
  18. Glover, E.D. and Sippel, R.F., 1967, Synthesis of magnesium calcite. Geochimica et Cosmochimica Acta, 31, 603–613.CrossRefGoogle Scholar
  19. Goldsmith, J.R., 1983, Phase relations of rhombohedral carbonates. In: Reeder, R.J. (ed.), Carbonates: Mineralogy and Chemistry. Reviews in Mineralogy, Mineralogical Society of America, Washington D.C., 11, p. 49–76.Google Scholar
  20. Goldsmith, J.R., Graf, D.L., and Joensuu, O.I., 1955, The occurrence of magnesian calcites in nature. Geochimica et Cosmochimica Acta, 7, 212–230.CrossRefGoogle Scholar
  21. Goldsmith, J.R. and Newton, R.C., 1969, P-T-X relations in the system CaCO3-MgCO3 at high temperatures and pressures. American Journal of Science: The Schairer, 267, 160–190.Google Scholar
  22. Goldsmith, J.R. and Graf, D.L., 1958, Relation between lattice constants and composition of the Ca-Mg carbonates. American Mineralogist, 43, 84–101.Google Scholar
  23. Goldsmith, J.R., Graf, D.L., and Heard, H.C., 1961, Lattice constants of the calcium-magnesium carbonates. American Mineralogist, 46, 453–457.Google Scholar
  24. Goldsmith, J.R. and Heard, H.C., 1961, Subsolidus phase relations in the system CaCO3-MgCO3. Journal of Geology, 69, 45–74.CrossRefGoogle Scholar
  25. Gunasekaran, S. and Anbalagan, G., 2007, Spectroscopic characterization of natural calcite minerals. Spectrochimica Acta Part A, 68, 656–664.CrossRefGoogle Scholar
  26. Harstad, A.O. and Stipp, S.L.S., 2007, Calcite dissolution: effects of trace cations naturally present in Iceland spar calcites. Geochimica et Cosmochimica Acta, 71, 56–70.CrossRefGoogle Scholar
  27. Hutcheon, I. and Moore, J.M., 1973, The tremolite isograde near Marble Lake, Ontario. Canadian Journal of Earth Sciences. 10, 936–947.CrossRefGoogle Scholar
  28. Kikuchi, C. and Matarrese, L.M., 1960, Paramagnetic resonance absorption of ions with spin 5/2: Mn++ in calcite. Journal of Chemical Physics, 33, 601–606.CrossRefGoogle Scholar
  29. Kretz, R., 1980, Occurrence, mineral chemistry, and metamorphism of Precambrian rocks in a portion of the Grenville province. Journal of Petrology, 21, 573–620.CrossRefGoogle Scholar
  30. Larson, A.C. and Dreele, R.B.V., 1994, General structure analysis system (GSAS). Los Alamos National Laboratory, Report LAUR, p. 86–748.Google Scholar
  31. Lear, C.H., Rosenthal, Y., and Slowey, N., 2002, Benthic foraminiferal Mg/Ca-paleothermometry: a revised core-top calibration. Geochimica et Cosmochimica Acta, 66, 3375–3387.CrossRefGoogle Scholar
  32. Mackenzie, F.T., Bischoff, W.D., Bishop, F.C., Loijens, M., Schoonmaker, J., and Wollast, R., 1983, Magnesian calcites: low-temperature occurrence, solubility and solid solution behavior. In: Reeder, R.J. (ed.), Carbonates: Mineralogy and Chemistry. Reviews in Mineralogy, Mineralogical Society of America, Washington D.C., 11, p. 97–144.Google Scholar
  33. Medeiros, S.K., Albuquerque, E.L., Maia, Jr.F.F., Caetano, E.W.S., and Freire, V.N., 2007, Electronic and optical properties of CaCO3 calcite, and excitons in Si@CaCO3 and CaCO3@SiO2 core-shell quantum dots. Journal of Physics D: Applied Physics, 40, 5747–5752.CrossRefGoogle Scholar
  34. Nesbitt, B.E. and Essene, E.J., 1980, Metamorphic thermometry and barometry of a portion of the Southern Blue Ridge province. American Journal of Science, 282, 701–729.CrossRefGoogle Scholar
  35. Nurnberg, D., 1995, Magnesium in test of Neogloboquadrina pachyderma sinistral from high northern and southern latitudes. Journal of Foraminiferal Research, 25, 350–368.CrossRefGoogle Scholar
  36. Puhan, D., 1976, Metamorphic temperature determined by means of the dolomite-calcite solvus geothermometer–examples from the central Damara Orogen (South West Africa). Contributions to Mineralogy and Petrology, 58, 23–28.CrossRefGoogle Scholar
  37. Rachlin, A.L., Henderson, G.S., and Goh, M.C., 1992, An atomic force microscope (AFM) study of the calcite cleavage plane: image averaging in Fourier space. American Mineralogist, 77, 904–910.Google Scholar
  38. Raz, S., Weiner, S., and Addadi, L., 2000, Formation of high-magnesian calcites via an amorphous precursor phase: possible biological implications. Advanced Materials, 12, 38–42.CrossRefGoogle Scholar
  39. Reeder, R.J. and Wenk, H.R., 1983, Structure refinements of some thermally disordered dolomites. American Mineralogist, 68, 769–776.Google Scholar
  40. Reeder, R.J. and Sheppard, C.E., 1984, Variations of lattice parameters in some sedimentary dolomites. American Mineralogist, 69, 520–527.Google Scholar
  41. Rice, J.M., 1977, Contact metamorphism of impure dolomitic limestone in the Boulder aureole, Montana. Contributions to Mineralogy and Petrology, 59, 237–259.CrossRefGoogle Scholar
  42. Rietveld, H.M., 1967, Line profiles of neutron powder-diffraction peaks for structure refinement. Acta Crystallographica, 22, 151–152.CrossRefGoogle Scholar
  43. Rietveld, H.M., 1969, A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography, 2, 65–71.CrossRefGoogle Scholar
  44. Rathmell, M.A., Streepey, M.M., Essene, E.J., and Van-der, P.B.A., 1999, Comparison of garnet-biotite, calcite-graphite, and calcite-dolomite thermometry in the Grenville Orogen: Ontario, Canada. Contributions to Mineralogy and Petrology, 134, 217–231.CrossRefGoogle Scholar
  45. Shen, C.C., Chiu, H.Y., Chiang, H.W., Chu, M.F., Wei, K.Y., Steinke, S., Chen, M.T., Lin, Y.S., and Lo, L., 2007, High precision measurements of Mg/Ca and Sr/Ca ratios in carbonates by cold plasma quadrupole mass spectrometry. Chemical Geology, 236, 339–349.CrossRefGoogle Scholar
  46. Skinner, A.J., Lafemina, J.P., and Jansen, H.J.F., 1994, Structure and bonding of calcite: a theoretical study. American Mineralogist, 79, 205–214.Google Scholar
  47. Titschack, J., Goetz-Neunhoeffer, F., and Neubauer, J., 2011, Magnesium quantification in calcite [(Ca,Mg)CO3] by Rietveld-based XRD analysis: Revisiting a well-established method. American Mineralogist, 96, 1028–1038.CrossRefGoogle Scholar
  48. Toby, B.H., 2001, EXPGUI, a graphical interface for GSAS. Journal of Applied Crystallography, 34, 210–213.CrossRefGoogle Scholar
  49. Tucker, M., 1988, Techniques in Sedimentology. Blackwell Scientific Publications, Oxford, 394 p.Google Scholar
  50. Wada, H. and Suzuki, K., 1983, Carbon isotopic thermometry calibrated by dolomite-calcite solvus temperatures. Geochimica et Cosmochimica Acta. 47, 697–606.CrossRefGoogle Scholar
  51. Zhang, F., Xu, H., Konishi, H., and Roden, E.E., 2010, A relationship between D104 value and composition in the calcite–disordered dolomite solid-solution series. American Mineralogist, 95, 1650–1656.CrossRefGoogle Scholar

Copyright information

© The Association of Korean Geoscience Societies and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Electrical EngineeringCOMSATS Institute of Information TechnologyAbbottabadPakistan
  2. 2.Department of PhysicsGC University LahoreLahorePakistan

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