Physics and Chemistry of Minerals

, Volume 45, Issue 2, pp 197–209 | Cite as

Raman spectroscopic study of synthetic pyrope–grossular garnets: structural implications

  • Wei Du
  • Baofu Han
  • Simon Martin Clark
  • Yichuan Wang
  • Xi Liu
Original Paper


A study of the effect of substitution of Mg and Ca in garnet solid solution (Grtss) was carried out using Raman spectroscopy to probe changes to the crystal lattice. The garnet solid solutions with composition changing along pyrope (Py; Mg3Al2Si3O12) and grossular (Gr; Ca3Al2Si3O12) binary were synthesized from glass at 6 GPa and 1400 °C and a second series of Grtss with composition Py40Gr60 were synthesized at 6 GPa but different temperatures from 1000 to 1400 °C. Raman mode assignments were made based on a comparison with the two end members pyrope and grossular, which show consistent result with literature study on single crystals data. The correlation between the Raman mode frequencies and compositional changes along the pyrope–grossular binary suggests a two-mode behavior for Mg and Ca cations in the garnet structure. The full widths at half-maximum of selected Raman modes increase on moving away from the end members and are about double the end-member values in the mid-position, where the frequencies closely linearly change with composition. The frequencies of the translational modes of the SiO4 tetrahedron (T(SiO4)) show large deviations from linearity indicating a strong kinematic coupling with the translational modes of the Ca and Mg cations. The anomalies in T(SiO4) are linked to mixing unit cell volume, suggesting that the nonlinear mixing volume behavior along the pyrope–grossular binary is related to the resistance of the Si–O bond to expansion and compression, which is caused by substitution of Mg and Ca cations in the dodecahedral sites. Annealing temperature also shows effect on Raman mode frequencies, but the main factor controlling the changes in mode frequencies along pyrope–grossular binary is composition.


Pyrope–grossular garnet solid solution Raman spectroscopy FWHM Non-ideal mixing Short-range ordering 



We thank two anonymous reviewers for their constructive comments on our manuscript and Dr. Larissa Dobrzhinetskaya for processing this paper. The authors thank Hongrui Ding from School of Earth and Space Sciences in Peking University for help with Raman Spectroscopy measurements. This work was supported by the Strategic Priority Research Program (B) of Chinese Academy of Sciences (Grant No. XDB18000000), and by the DREAM project of MOST, China (Grant No. 2016YFC0600408) to Xi Liu.


  1. Armbruster T, Geiger CA, Lager GA (1992) Single crystal X-ray refinement of almandine-pyrope garnets at 298 and 100 K. Am Min 77:512–523Google Scholar
  2. Baima J, Ferrabone M, Orlando R, Erba A, Dovesi R (2015) Thermodynamics and phonon dispersion of pyrope and grossular silicate garnets from ab initio simulations. Phys Chem Min 43:137–149CrossRefGoogle Scholar
  3. Boffa Ballaran T, Woodland AB (2006) Local structure of ferric iron-bearing garnets deduced by IR-spectroscopy. Chem Geol 225:360–372CrossRefGoogle Scholar
  4. Boffa Ballaran T, Carpenter MA, Geiger CA, Koziol AM (1999) Local structural heterogeneity in garnet solid solutions. Phys Chem Mineral 26:554–569CrossRefGoogle Scholar
  5. Bosenick A, Geiger CA, Schaller T, Sebald A (1995) A 29Si MAS NMR and IR spectroscopic investigation of synthetic pyrope-grossular garnet solid solutions. Am Min 80:691–704CrossRefGoogle Scholar
  6. Bosenick A, Geiger CA, Phillips BL (1999) Local Ca-Mg distribution of Mg-rich pyrope-grossular garnets synthesized at different temperatures revealed by 29Si MAS NMR spectroscopy. Am Min 84:1422–1432CrossRefGoogle Scholar
  7. Bosenick A, Dove MT, Geiger CA (2000) Simulation studies on the pyrope-grossular garnet solid solution. Phys Chem Min 27:398–418CrossRefGoogle Scholar
  8. Bosenick A, Dove MT, Heine V, Geiger CA (2001) Scaling of thermodynamic mixing properties in garnet solid solutions. Phys Chem Min 28:177–187CrossRefGoogle Scholar
  9. Dachs E, Geiger CA (2006) Heat capacities and entropies of mixing of pyrope-grossular (Mg3Al2Si3O12–Ca3Al2Si3O12) garnet solid solutions: a low-temperature calorimetric and a thermodynamic investigation. Am Min 91:894–906CrossRefGoogle Scholar
  10. Dove MT (2001) Computer simulations of solid solutions. In: Geiger CA (ed) Solid solutions in silicate and oxide systems of geological importance. EMU notes in mineralogy, vol 3. Eötvös University Press, Budapest, pp 225–250Google Scholar
  11. Dove MT, Bosenick A, Myers ER, Warren MC, Redfer SAT (2000) Modeling in relation to cation ordering. Phase Trans 71:205–226CrossRefGoogle Scholar
  12. Du W, Clark SM, Walker D (2015) Thermo-compression of pyrope-grossular garnet solid solution: non-linear compositional dependence. Am Min 100:215–222CrossRefGoogle Scholar
  13. Du W, Clark SM, Walker D (2016) Excess mixing volume, microstrain, and stability of pyrope-grossular garnets. Am Min 101:193–204CrossRefGoogle Scholar
  14. Du W, Li X, Li B (2017) Microstrain in pyrope-grossular garnet solid solution at high pressure: a case study of Py90Gr10 and Py10Gr90 up to 15 GPa. Phys Chem Min 44(6):377–388CrossRefGoogle Scholar
  15. Freeman CL, Allan NL, van Westrenen W (2006) Local cation environments in the pyrope-grossular Mg3Al2Si3O12–Ca3Al2Si3O12 garnet solid solution. Phys Rev B 74:134203CrossRefGoogle Scholar
  16. Ganguly J, Cheng W, O’Neill HC (1993) Syntheses, volume, and structural changes of garnets in the pyrope-grossular join; implications for stability and mixing properties. Am Min 78:583–593Google Scholar
  17. Geiger CA, Feenstra A (1997) Molar volumes of mixing of almandine-pyrope and almandine-spessartine garnets and the crystal chemistry and thermodynamic-mixing properties of the aluminosilicate garnets. Am Min 82:571–581CrossRefGoogle Scholar
  18. Geiger CA, Newton RC, Kleppa OJ (1987) Enthalpy of mixing of synthetic almandine-grossular and almandine-pyrope garnets from high-temperature solution calorimetry. Geochim Cosmochim Acta 51:1755–1763CrossRefGoogle Scholar
  19. Gillet P, Fiquet G, Malezieux JM, Geiger CA (1992) High-pressure and high-temperature Raman spectroscopy of end-member garnets: pyrope, grossular and andradite. Eur J Min 4:651–664CrossRefGoogle Scholar
  20. Hofmeister AM, Chopelas A (1991a) Vibrational spectroscopy of end-member silicate garnets. Phys Chem Min 17:503–526CrossRefGoogle Scholar
  21. Hofmeister AM, Chopelas A (1991b) Thermodynamic properties of pyrope and grossular from vibrational spectroscopy. Am Min 76:880–891Google Scholar
  22. Irifune T, Ringwood AE (1987) Phase transformation in primitive MORB and pyrolite compositions to 25 GPa and some geophysical implications. In: Manghnani MH, Syono Y (eds) High pressure research in mineral physics, vol 39. TERRAPUB Tokyo/American Geophysical Union, Washington, DC, pp 235–246Google Scholar
  23. Irifune T, Ringwood AE (1993) Phase transformations in subducted oceanic crust and buoyancy relationships at depths of 600–800 km in the mantle. Earth Planet Sci Lett 117(1–2):101–110CrossRefGoogle Scholar
  24. Kelsey KE, Stebbins JF, Du L, Mosenfelder JL, Asimow PD, Geiger CA (2008) Cation order/disorder behavior and crystal chemistry of pyrope-grossular garnets: an 17O 3QMAS and 27Al MAS NMR spectroscopic study. Am Min 93:134–143CrossRefGoogle Scholar
  25. Kolesov BA, Geiger CA (1998) Raman spectra of silicate garnets. Phys Chem Min 25:142–151CrossRefGoogle Scholar
  26. Kolesov BA, Geiger CA (2000) Low-temperature single-crystal Raman spectrum of pyrope. Phys Chem Min 27:645–649CrossRefGoogle Scholar
  27. Langford JI, Wilson AJC (1978) Scherrer after sixty years: a survey and some new results in the determination of crystallite size. J Appl Crystallogr 11:102–113CrossRefGoogle Scholar
  28. Lavrentiev MY, van Westrenen W, Allan NL, Freeman CL, Purton JA (2006) Simulation of thermodynamic mixing properties of garnet solid solutions at high temperatures and pressures. Chem Geol 225:336–346CrossRefGoogle Scholar
  29. Liu Z, Du W, Shinme T, Gréaux S, Zhou C, Arimoto T, Kunimoto T, Irifune T (2017) Garnets in the majorite-pyrope system: symmetry, lattice microstrain, and order-disorder of cations. Phys Chem Min 44:237–245CrossRefGoogle Scholar
  30. Mernagh TP, Liu L (1990) Pressure dependence of Raman spectra from the garnet end-members pyrope, grossularite and almandine. J Raman Spec 21:305–309CrossRefGoogle Scholar
  31. Nakatsuka A, Shimokawa M, Nakayama N, Ohtaka O, Arima H, Okube M, Yoshiasa A (2011) Static disorders of atoms and experimental determination of Debye temperature in pyrope: low- and high-temperature single-crystal X-ray diffraction study. Am Min 96:1593–1605CrossRefGoogle Scholar
  32. Newton RC, Charlu TV, Kleppa OJ (1977) Thermochemistry of high pressure garnets and clinopyroxenes in the system CaO-MgO-Al2O3-SiO2. Geochim Cosmochim Acta 41:369–377CrossRefGoogle Scholar
  33. Oberti R, Quartieri S, Dalconi MC, Boscherini F, Iezzi G, Boiocchi M, Eeckhout SG (2006) Site preference and local geometry of Sc in garnets: part I. Multifarious mechanisms in the pyrope-grossular join. Am Min 91:1230–1239CrossRefGoogle Scholar
  34. Quartieri S, Boscherini F, Dalconi C, Iezzi G, Meneghini C, Oberti R (2008) Magnesium K-edge EXAFS study of bond-length behavior in synthetic pyrope-grossular garnet solid solutions. Am Min 93:495–498CrossRefGoogle Scholar
  35. Scherrer P (1918) Bestimmung der Grösse und der inneren Struktur von Kolloidteilchen mittels Röntgenstrahlen. Nachrichten der Kgl Gesellschaft der Wissenschaftern zu Göttingen 26:98–100Google Scholar
  36. Shannon RD (1976) Revised effective ionic radii. Acta Crystallogr A32:751–767CrossRefGoogle Scholar
  37. Stokes AR, Wilson AC (1944) The diffraction of X rays by distorted crystal aggregates. Proc Phys Soc 56:174–181CrossRefGoogle Scholar
  38. van Westrenen W, Blundy J, Wood B (1999) Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am Min 84:838–847CrossRefGoogle Scholar
  39. Vegard L (1921) Die Konstitution der Mischkristalle und die Raumfüllung der Atome. Zeitschrift für Physik 5:17–26CrossRefGoogle Scholar
  40. Vinograd VL, Sluiter MHF (2006) Thermodynamics of mixing in pyrope-grossular, Mg3Al2Si3O12-Ca3Al2Si3O12, solid solution from lattice dynamics calculations and Monte Carlo simulations. Am Min 91:1815–1830CrossRefGoogle Scholar
  41. Vinograd VL, Sluiter M, Winkler B, Putnis A, Hålenius U, Gale JD, Becker U (2004) Thermodynamics of mixing and ordering in pyrope-grossular solid solution. Min Mag 68:101–121CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  • Wei Du
    • 1
    • 2
    • 3
  • Baofu Han
    • 1
    • 2
  • Simon Martin Clark
    • 4
  • Yichuan Wang
    • 1
    • 2
  • Xi Liu
    • 1
    • 2
  1. 1.Key Laboratory of Orogenic Belts and Crustal Evolution, MOEPeking UniversityBeijingChina
  2. 2.School of Earth and Space SciencesPeking UniversityBeijingChina
  3. 3.Lamont-Doherty Earth ObservatoryColumbia University in the City of New YorkNew YorkUSA
  4. 4.Department of Earth and Planetary SciencesMacquarie UniversityNorth RydeAustralia

Personalised recommendations