Home Depth of formation of super-deep diamonds: Raman barometry of CaSiO3-walstromite inclusions
Article
Licensed
Unlicensed Requires Authentication

Depth of formation of super-deep diamonds: Raman barometry of CaSiO3-walstromite inclusions

  • Chiara Anzolini EMAIL logo , Mauro Prencipe , Matteo Alvaro , Claudia Romano , Alessandro Vona , Sofia Lorenzon , Evan M. Smith , Frank E. Brenker and Fabrizio Nestola
Published/Copyright: January 2, 2018
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 103 Issue 1

Abstract

“Super-deep” diamonds are thought to have a sub-lithospheric origin (i.e., below ~300 km depth) because some of the mineral phases entrapped within them as inclusions are considered to be the products of retrograde transformation from lower-mantle or transition-zone precursors. CaSiO3-walstromite, the most abundant Ca-bearing mineral inclusion found in super-deep diamonds, is believed to derive from CaSiO3-perovskite, which is stable only below ~600 km depth, although its real depth of origin is controversial. The remnant pressure (Pinc) retained by an inclusion, combined with the thermoelastic parameters of the mineral inclusion and the diamond host, allows calculation of the entrapment pressure of the diamond-inclusion pair. Raman spectroscopy, together with X-ray diffraction, is the most commonly used method for measuring the Pinc without damaging the diamond host.

In the present study we provide, for the first time, a calibration curve to determine the Pinc of a CaSiO3-walstromite inclusion by means of Raman spectroscopy without breaking the diamond. To do so, we performed high-pressure micro-Raman investigations on a CaSiO3-walstromite crystal under hydrostatic stress conditions within a diamond-anvil cell. We additionally calculated the Raman spectrum of CaSiO3-walstromite by ab initio methods both under hydrostatic and non-hydrostatic stress conditions to avoid misinterpretation of the results caused by the possible presence of deviatoric stresses causing anomalous shift of CaSiO3-walstromite Raman peaks. Last, we applied single-inclusion elastic barometry to estimate the minimum entrapment pressure of a CaSiO3-walstromite inclusion trapped in a natural diamond, which is ~9 GPa (~260 km) at 1800 K. These results suggest that the diamond investigated is certainly sub-lithospheric and endorse the hypothesis that the presence of CaSiO3-walstromite is a strong indication of super-deep origin.

Keywords: Diamond; inclusion; CaSiO3-walstromite; micro-Raman spectroscopy; ab initio methods; elastic geobarometry

Acknowledgments

This investigation was financially supported by Fondazione Cassa di Risparmio di Padova e Rovigo and by the project INDIMEDEA, funded by the ERC-StG 2012 to F.N. (Grant No. 307322). M.A. has been supported by the Italian SIR-MIUR MILE DEEp (Grant No. RBSI140351) and the ERC-StG 2016 TRUE DEPTHS (Grant No. 714936). Ross J. Angel is thanked for advice and discussion. We are also grateful to H.M. Lamadrid for reviewing the manuscript.

References Cited

Angel, R.J., Alvaro, M., and Gonzalez-Platas, J. (2014a) EosFit7c and a Fortran module (library) for equation of state calculations. Zeitschrift für Kristallographie- Crystalline Materials, 229, 405–419.10.1515/zkri-2013-1711Search in Google Scholar

Angel, R.J., Mazzucchelli, M.L., Alvaro, M., Nimis, P., and Nestola, F. (2014b) Geobarometry from host-inclusion systems: The role of elastic relaxation. American Mineralogist, 99, 2146–2149.10.2138/am-2014-5047Search in Google Scholar

Angel, R.J., Alvaro, M., Nestola, F., and Mazzucchelli, M.L. (2015a) Diamond thermoelastic properties and implications for determining the pressure of formation of diamond-inclusion systems. Russian Geology and Geophysics, 56, 211–220.10.1016/j.rgg.2015.01.014Search in Google Scholar

Angel, R.J., Nimis, P., Mazzucchelli, M.L., Alvaro, M., and Nestola, F. (2015b) How large are departures from lithostatic pressure? Constraints from host–inclusion elasticity. Journal of Metamorphic Geology, 33, 801–813.10.1111/jmg.12138Search in Google Scholar

Anzolini, C., Angel, R.J., Merlini, M., Derzsi, M., Tokár, K., Milani, S., Krebs, M.Y., Brenker, F.E., Nestola, F., and Harris, J.W. (2016) Depth of formation of CaSiO3-walstromite included in super-deep diamonds. Lithos, 265, 138–147.10.1016/j.lithos.2016.09.025Search in Google Scholar

Artioli, G., Angelini, I., and Polla, A. (2008) Crystals and phase transitions in protohistoric glass materials. Phase Transitions, 81, 233–252.10.1080/01411590701514409Search in Google Scholar

Brenker, F.E., Stachel, T., and Harris, J.W. (2002) Exhumation of lower mantle inclusions in diamond: ATEM investigation of retrograde phase transitions, reactions and exsolution. Earth and Planetary Science Letters, 198, 1–9.10.1016/S0012-821X(02)00514-9Search in Google Scholar

Brenker, F.E., Vincze, L., Vekemans, B., Nasdala, L., Stachel, T., Vollmer, C., Kersten, M., Somogyi, A., Adams, F., and Joswig, W. (2005) Detection of a Ca-rich lithology in the Earth’s deep (>300 km) convecting mantle. Earth and Planetary Science Letters, 236, 579–587.10.1016/j.epsl.2005.05.021Search in Google Scholar

Brenker, F.E., Vollmer, C., Vincze, L., Vekemans, B., Szymanski, A., Janssens, K., Szaloki, I., Nasdala, L., Joswig, W., and Kaminsky, F. (2007) Carbonates from the lower part of transition zone or even the lower mantle. Earth and Planetary Science Letters, 260, 1–9.10.1016/j.epsl.2007.02.038Search in Google Scholar

Civalleri, B., D’Arco, P., Orlando, R., Saunders, V., and Dovesi, R. (2001) Hartree–Fock geometry optimisation of periodic systems with the CRYSTAL code. Chemical Physics Letters, 348, 131–138.10.1016/S0009-2614(01)01081-8Search in Google Scholar

Day, H.W. (2012) A revised diamond-graphite transition curve. American Mineralogist, 97, 52–62.10.2138/am.2011.3763Search in Google Scholar

Dovesi, R., Saunders, V., Roetti, C., Orlando, R., Zicovich-Wilson, C., Pascale, F., Civalleri, B., Doll, K., Harrison, N., and Bush, I. (2014) CRYSTAL14 User’s Manual. University of Torino, Italy.Search in Google Scholar

Eshelby, J.D. (1957) The determination of the elastic field of an ellipsoidal inclusion, and related problems. In Proceedings of the Royal Society of London A: Mathematical, Physical and Engineering Sciences, 376–396. The Royal Society.10.1098/rspa.1957.0133Search in Google Scholar

Eshelby, J.D. (1959) The elastic field outside an ellipsoidal inclusion. In Proceedings of the Royal Society of London A: Mathematical, Physical and Engineering Sciences, 561–569. The Royal Society.10.1098/rspa.1959.0173Search in Google Scholar

Essene, E. (1974) High-pressure transformations in CaSiO3. Contributions to Mineralogy and Petrology, 45, 247–250.10.1007/BF00383442Search in Google Scholar

Frost, D.J. (2008) The upper mantle and transition zone. Elements, 4, 171–176.10.2113/GSELEMENTS.4.3.171Search in Google Scholar

Gasparik, T., Wolf, K., and Smith, C.M. (1994) Experimental determination of phase relations in the CaSiO3 system from 8 to 15 GPa. American Mineralogist, 79, 1219–1222.Search in Google Scholar

Harte, B. (2010) Diamond formation in the deep mantle: the record of mineral inclusions and their distribution in relation to mantle dehydration zones. Mineralogical Magazine, 74, 189–215.10.1180/minmag.2010.074.2.189Search in Google Scholar

Howell, D., Wood, I.G., Nestola, F., Nimis, P., and Nasdala, L. (2012) Inclusions under remnant pressure in diamond: a multi-technique approach. European Journal of Mineralogy, 4, 563–573.10.1127/0935-1221/2012/0024-2183Search in Google Scholar

Irifune, T., and Ringwood, A. (1987) Phase transformations in a harzburgite composition to 26 GPa: implications for dynamical behaviour of the subducting slab. Earth and Planetary Science Letters, 86, 365-376.10.1016/0012-821X(87)90233-0Search in Google Scholar

Izraeli, E., Harris, J., and Navon, O. (1999) Raman barometry of diamond formation. Earth and Planetary Science Letters, 173, 351–360.10.1016/S0012-821X(99)00235-6Search in Google Scholar

Joswig, W., Stachel, T., Harris, J.W., Baur, W.H., and Brey, G.P. (1999) New Ca-silicate inclusions in diamonds—tracers from the lower mantle. Earth and Planetary Science Letters, 173, 1–6.10.1016/S0012-821X(99)00210-1Search in Google Scholar

Kaminsky, F. (2012) Mineralogy of the lower mantle: A review of “super-deep” mineral inclusions in diamond. Earth-Science Reviews, 110, 127–147.10.1016/j.earscirev.2011.10.005Search in Google Scholar

Lee, C., Yang, W., and Parr, R.G. (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical review B, 37, 785.10.1103/PhysRevB.37.785Search in Google Scholar PubMed

Mao, H., Xu, J., and Bell, P. (1986) Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions. Journal of Geophysical Research: Solid Earth, 91, 4673–4676.10.1029/JB091iB05p04673Search in Google Scholar

Maschio, L., Kirtman, B., Orlando, R., and Rèrat, M. (2012) Ab initio analytical infrared intensities for periodic systems through a coupled perturbed Hartree- Fock/Kohn-Sham method. The Journal of Chemical Physics, 137, 204113.10.1063/1.4767438Search in Google Scholar PubMed

Maschio, L., Kirtman, B., Rérat, M., Orlando, R., and Dovesi, R. (2013) Ab initio analytical Raman intensities for periodic systems through a coupled perturbed Hartree-Fock/Kohn-Sham method in an atomic orbital basis. I. Theory. The Journal of Chemical Physics, 139, 164101.10.1063/1.4824442Search in Google Scholar PubMed

Mazzucchelli, M.L., Angel, R.J., Rustioni, G., Milani, S., Nimis, P., Domeneghetti, M.C., Marone, F., Harris, J.W., Nestola, F., and Alvaro, M. (2016) Elastic geobarometry and the role of brittle failure on pressure release. In EGU General Assembly Conference Abstracts, 13569.Search in Google Scholar

Mazzucchelli, M.L., Burnley, P.C., Angel, R.J., Domeneghetti, M.C., Nestola, F., and Alvaro, M. (2017) Elastic geobarometry: uncertainties arising from the geometry of the host-inclusion system. In EGU General Assembly Conference Abstracts, 2060.Search in Google Scholar

Milani, S., Nestola, F., Angel, R., Nimis, P., and Harris, J. (2016) Crystallographic orientations of olivine inclusions in diamonds. Lithos, 265, 312–316.10.1016/j.lithos.2016.06.010Search in Google Scholar

Monkhorst, H.J., and Pack, J.D. (1976) Special points for Brillouin-zone integrations. Physical Review B, 13, 5188.10.1103/PhysRevB.13.5188Search in Google Scholar

Nasdala, L., Brenker, F.E., Glinnemann, J., Hofmeister, W., Gasparik, T., Harris, J.W., Stachel, T., and Reese, I. (2003) Spectroscopic 2D-tomography Residual pressure and strain around mineral inclusions in diamonds. European Journal of Mineralogy, 15, 931–935.10.1127/0935-1221/2003/0015-0931Search in Google Scholar

Nestola, F., Merli, M., Nimis, P., Parisatto, M., Kopylova, M., De Stefano, A., Longo, M., Ziberna, L., and Manghnani, M. (2012) In situ analysis of garnet inclusion in diamond using single-crystal X-ray diffraction and X-ray microtomography. European Journal of Mineralogy, 24, 599–606.10.1127/0935-1221/2012/0024-2212Search in Google Scholar

Nestola, F., Nimis, P., Angel, R., Milani, S., Bruno, M., Prencipe, M., and Harris, J. (2014) Olivine with diamond-imposed morphology included in diamonds. Syngenesis or protogenesis?. International Geology Review, 56, 1658–1667.10.1080/00206814.2014.956153Search in Google Scholar

Nestola, F., Burnham, A.D., Peruzzo, L., Tauro, L., Alvaro, M., Walter, M.J., Gunter, M., Anzolini, C., and Kohn, S.C. (2016) Tetragonal Almandine-Pyrope Phase, TAPP: finally a name for it, the new mineral jeffbenite. Mineralogical Magazine, 80, 1219–1232.10.1180/minmag.2016.080.059Search in Google Scholar

Nestola, F., Jung, H. and Taylor, L.A. (2017) Mineral inclusions in diamonds may be synchronous but not syngenetic. Nature Communications, 14168.10.1038/ncomms14168Search in Google Scholar

Nimis, P., Alvaro, M., Nestola, F., Angel, R.J., Marquardt, K., Rustioni, G., Harris, J.W., and Marone, F. (2016) First evidence of hydrous silicic fluid films around solid inclusions in gem-quality diamonds. Lithos, 260, 384–389.10.1016/j.lithos.2016.05.019Search in Google Scholar

Pascale, F., Zicovich-Wilson, C.M., Lopez Gejo, F., Civalleri, B., Orlando, R., and Dovesi, R. (2004) The calculation of the vibrational frequencies of crystalline compounds and its implementation in the CRYSTAL code. Journal of Computational Chemistry, 25, 888–897.10.1002/jcc.20019Search in Google Scholar

Pearson, D., Brenker, F., Nestola, F., McNeill, J., Nasdala, L., Hutchison, M., Matveev, S., Mather, K., Silversmit, G., and Schmitz, S. (2014) Hydrous mantle transition zone indicated by ringwoodite included within diamond. Nature, 507, 221–224.10.1038/nature13080Search in Google Scholar

Ringwood, A. (1991) Phase transformations and their bearing on the constitution and dynamics of the mantle. Geochimica et Cosmochimica Acta, 55, 2083–2110.10.1016/0016-7037(91)90090-RSearch in Google Scholar

Stachel, T., and Harris, J. (2008) The origin of cratonic diamonds—constraints from mineral inclusions. Ore Geology Reviews, 34, 5–32.10.1016/j.oregeorev.2007.05.002Search in Google Scholar

Turcotte, D., and Schubert, G. (2014) Geodynamics, 3rd ed. Cambridge University Press.10.1017/CBO9780511843877Search in Google Scholar

Van der Molen, I., and Van Roermund, H. (1986) The pressure path of solid inclusions in minerals: the retention of coesite inclusions during uplift. Lithos, 19, 317–324.10.1016/0024-4937(86)90030-7Search in Google Scholar

Wu, Z., and Cohen, R.E. (2006) More accurate generalized gradient approximation for solids. Physical Review B, 73, 235116.10.1103/PhysRevB.73.235116Search in Google Scholar

Received: 2017-5-8
Accepted: 2017-9-25
Published Online: 2018-1-2
Published in Print: 2018-1-26

© 2018 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  2. The third isotope of the third element on the third planet
  4. Visible, near-infrared, and mid-infrared spectral characterization of Hawaiian fumarolic alteration near Kilauea’s December 1974 flow: Implications for spectral discrimination of alteration environments on Mars
  6. Magnetite-apatite deposit from Sri Lanka: Implications on Kiruna-type mineralization associated with ultramafic intrusion and mantle metasomatism
  8. The ore-forming magmatic-hydrothermal system of the Piaotang W-Sn deposit (Jiangxi, China) as seen from Li-mica geochemistry
  10. Chlorine incorporation into amphibole and biotite in high-grade iron-formations: Interplay between crystallography and metamorphic fluids
  12. Depth of formation of super-deep diamonds: Raman barometry of CaSiO3-walstromite inclusions
  14. Microtexture investigation of amblygonite–montebrasite series with lacroixite: Characteristics and formation process in pegmatites
  16. Sound velocity measurements of hcp Fe-Si alloy at high pressure and high temperature by inelastic X-ray scattering
  18. New insights into the metallogeny of MVT Zn-Pb deposits: A case study from the Nayongzhi in South China, using field data, fluid compositions, and in situ S-Pb isotopes
  20. Slow weathering of a sandstone-derived Podzol (Falkland Islands) resulting in high content of a non-crystalline silicate
  22. Mineralogy, paragenesis, and mineral chemistry of REEs in the Olserum-Djupedal REE-phosphate mineralization, SE Sweden
  24. Leesite, K(H2O)2[(UO2)4O2(OH)5]·3H2O, a new K-bearing schoepite-family mineral from the Jomac mine, San Juan County, Utah, U.S.A
  26. Chromium-bearing phases in the Earth’s mantle: Evidence from experiments in the Mg2SiO4–MgCr2O4 system at 10–24 GPa and 1600 °C
  27. Crossroads in Earth and Planetary Materials
  28. High-pressure phase transitions in MgCr2O4·Mg2SiO4 composition: Reactions between olivine and chromite with implications for ultrahigh-pressure chromitites
  29. Letter
  30. A novel carbon bonding environment in deep mantle high-pressure dolomite
  31. Letter
  32. Structuration under pressure: Spatial separation of inserted water during pressure-induced hydration in mesolite
  33. Book Review
  34. Book Review: The International Atlas of Mars Exploration: From Spirit to Curiosity
https://doi.org/10.2138/am-2018-6184
Keywords for this article
Diamond; inclusion; CaSiO3-walstromite; micro-Raman spectroscopy; ab initio methods; elastic geobarometry

Articles in the same Issue

  2. The third isotope of the third element on the third planet
  4. Visible, near-infrared, and mid-infrared spectral characterization of Hawaiian fumarolic alteration near Kilauea’s December 1974 flow: Implications for spectral discrimination of alteration environments on Mars
  6. Magnetite-apatite deposit from Sri Lanka: Implications on Kiruna-type mineralization associated with ultramafic intrusion and mantle metasomatism
  8. The ore-forming magmatic-hydrothermal system of the Piaotang W-Sn deposit (Jiangxi, China) as seen from Li-mica geochemistry
  10. Chlorine incorporation into amphibole and biotite in high-grade iron-formations: Interplay between crystallography and metamorphic fluids
  12. Depth of formation of super-deep diamonds: Raman barometry of CaSiO3-walstromite inclusions
  14. Microtexture investigation of amblygonite–montebrasite series with lacroixite: Characteristics and formation process in pegmatites
  16. Sound velocity measurements of hcp Fe-Si alloy at high pressure and high temperature by inelastic X-ray scattering
  18. New insights into the metallogeny of MVT Zn-Pb deposits: A case study from the Nayongzhi in South China, using field data, fluid compositions, and in situ S-Pb isotopes
  20. Slow weathering of a sandstone-derived Podzol (Falkland Islands) resulting in high content of a non-crystalline silicate
  22. Mineralogy, paragenesis, and mineral chemistry of REEs in the Olserum-Djupedal REE-phosphate mineralization, SE Sweden
  24. Leesite, K(H2O)2[(UO2)4O2(OH)5]·3H2O, a new K-bearing schoepite-family mineral from the Jomac mine, San Juan County, Utah, U.S.A
  26. Chromium-bearing phases in the Earth’s mantle: Evidence from experiments in the Mg2SiO4–MgCr2O4 system at 10–24 GPa and 1600 °C
  27. Crossroads in Earth and Planetary Materials
  28. High-pressure phase transitions in MgCr2O4·Mg2SiO4 composition: Reactions between olivine and chromite with implications for ultrahigh-pressure chromitites
  29. Letter
  30. A novel carbon bonding environment in deep mantle high-pressure dolomite
  31. Letter
  32. Structuration under pressure: Spatial separation of inserted water during pressure-induced hydration in mesolite
  33. Book Review
  34. Book Review: The International Atlas of Mars Exploration: From Spirit to Curiosity
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 23.10.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2018-6184/html
Scroll to top button