Skip to main content

Advertisement

SpringerLink
Log in

High-pressure neutron diffraction study on H–D isotope effects in brucite

  • Original Paper
  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

A neutron powder diffraction study of hydrogenated and deuterated brucite was conducted at ambient temperature and at pressures up to 9 GPa, using a Paris–Edinburgh high-pressure cell at the WAND instrument of the ORNL High Flux Isotope Reactor. The two materials were synthesized by the same method and companion measurements of neutron diffraction were conducted under the same conditions. Our refinement results show that the lattice-parameters of the a axis, parallel to the sheets of Mg–O octahedra, decrease only slightly with pressure with no effect of H–D substitution. However, the c axis of Mg(OD)2 is shorter and may exhibit greater compressibility with pressure than that of Mg(OH)2. Consequently, the unit-cell volume of deuterated brucite is slightly, but systematically smaller than that of hydrogenated brucite. When fitted to a third-order Birch–Murnaghan equation in terms of the normalized unit-cell volume, values of the bulk modulus for hydrogenated and deuterated brucite (K 0 = 39.0 ± 2.8 and 40.4 ± 1.3 GPa, respectively) are, however, indistinguishable from each other within the experimental errors. The measured effect of H–D substitution on the unit-cell volume also demonstrates that brucite (and other hydrous minerals) preferentially incorporate deuterium over hydrogen under pressure, suggesting that the distribution of hydrogen isotopes in deep-earth conditions may differ significantly from that in near-surface environments.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Angel RJ (2000) Equations of state. In: Hazen RM, Downs RT (eds) High-pressure and high-temperature crystal chemistry. MSA Reviews in Mineralogy and Geochemistry, vol 41, pp 35–59

  • Catti M, Ferraris G, Hull S, Pavese A (1995) Static compression and H-disorder in Brucite, Mg(OH)2, to 11 GPa—a powder neutron-diffraction study. Phys Chem Mineral 22(3):200–206

    Google Scholar 

  • Chakoumakos BC, Loong CK, Schultz AJ (1997) Low-temperature structure and dynamics of brucite. J Phys Chem B 101(46):9458–9462

    Article  Google Scholar 

  • Decker DL (1971) High-pressure equation of state for NaCl, KCl, and CsCl. J Appl Phys 42(8):3239–3244

    Article  Google Scholar 

  • Desgranges L, Calvarin G, Chevrier G (1996) Interlayer interactions in M(OH)2: a neutron diffraction study of Mg(OH)2. Acta Crystallogr B 52:82–86

    Article  Google Scholar 

  • Duffy TS, Ahrens TJ (1991) The shock-wave equation of state of brucite Mg(OH)2. J Geophys Res 96B:14319–14330

    Article  Google Scholar 

  • Duffy TS, Shu JF, Mao HK, Hemley RJ (1995) Single-crystal X-ray-diffraction of brucite to 14 GPa. Phys Chem Mineral 22(5):277–281

    Google Scholar 

  • Fei YW, Mao HK (1993) Static Compression of Mg(OH)2 to 78-GPa at High-Temperature and Constraints on the Equation of State of Fluid H2O. J Geophys Res 98(B7):11875–11884

    Article  Google Scholar 

  • Fukui H, Ohtaka O, Suzuki T, Funakoshi K (2003) Thermal expansion of Mg(OH)2 brucite under high pressure and pressure dependence of entropy. Phys Chem Mineral 30(9):511–516

    Article  Google Scholar 

  • Hermansson K, Gajewski G, Mitev PD (2008) Pressure-induced OH frequency downshift in brucite: frequency-distance and frequency-field correlations. J Phys 117:1–8

    Google Scholar 

  • Horita J, Cole DR, Polyakov VB, Driesner T (2002) Experimental and theoretical study of pressure effects on hydrogen isotope fractionation in the system brucite-water at elevated temperatures. Geochim Cosmochim Acta 66(21):3769–3788

    Article  Google Scholar 

  • Jayachandran KP, Liu LG (2006) High pressure elasticity and phase transformation in brucite, Mg(OH)2. Phys Chem Mineral 33(7):484–489

    Article  Google Scholar 

  • Jiang FM, Speziale S, Duffy TS (2006) Single-crystal elasticity of brucite, Mg(OH)2, to 15 GPa by Brillouin scattering. Am Mineral 91(11–12):1893–1900

    Article  Google Scholar 

  • Kruger MB, Williams Q, Jeanloz R (1989) Vibrational-Spectra of Mg(OH)2 and Ca(OH)2 under Pressure. J Chem Phys 91(10):5910–5915

    Article  Google Scholar 

  • Mitev PD, Gajewski G, Hermansson K (2009) Anharmonic OH vibrations in brucite: small pressure-induced redshift in the range 0–22 GPa. Am Mineral 94(11–12):1687–1697

    Article  Google Scholar 

  • Mookherjee M, Stixrude L (2006) High-pressure proton disorder in brucite. Am Mineral 91(1):127–134

    Article  Google Scholar 

  • Nagai T, Hattori T, Yamanaka T (2000) Compression mechanism of brucite: an investigation by structural refinement under pressure. Am Mineral 85(5–6):760–764

    Google Scholar 

  • Parise JB, Leinenweber K, Weidner DJ, Tan K, Vondreele RB (1994) Pressure-induced H-bonding—neutron-diffraction study of brucite, Mg(OD)2, to 9.3 GPa. Am Mineral 79(1–2):193–196

    Google Scholar 

  • Polyakov VB, Horita J, Cole DR (2006) Pressure effects on the reduced partition function ratio for hydrogen isotopes in water. Geochim Cosmochim Acta 70(8):1904–1913

    Article  Google Scholar 

  • Raugei S, Silvestrelli PL, Parrinello M (1999) Pressure-induced frustration and disorder in Mg(OH)2 and Ca(OH)2. Phys Rev Lett 83(11):2222–2225

    Article  Google Scholar 

  • Reynard B, Caracas R (2009) D/H isotopic fractionation between brucite Mg(OH)(2) and water from first-principles vibrational modeling. Chem Geol 262(3–4):159–168

    Article  Google Scholar 

  • Rodriguez-Carvajal J (1993) Recent advances in magnetic-structure determination by neutron powder diffraction. Physica B 192(1–2):55–69

    Article  Google Scholar 

  • Rupke L, Morgan JP, Dixon JE (2006) Implications of subduction rehydration for earth’s deep water cycle. In: Jacobsen SD, Van der Lee S (eds) Earth’s deep water cycle. American Geophysical Union, Washington, DC, pp 263–276

    Google Scholar 

  • Sano-Furukawa A, Kagi H, Nagai T, Nakano S, Fukura S, Ushijima D, Iizuka R, Ohtani E, Yagi T (2009) Change in compressibility of δ-AlOOH and δ-AlOOD at high pressure: a study of isotope effect and hydrogen-bond symmetrization. Am Mineral 94(8–9):1255–1261

    Article  Google Scholar 

  • Saxena SK (1989) Assessment of bulk modulus, thermal-expansion and heat-capacity of minerals. Geochim Cosmochim Acta 53(4):785–789

    Article  Google Scholar 

  • Sherman DM (1991) Hartree–Fock band-structure, equation of state, and pressure-induced hydrogen-bonding in brucite, Mg(OH)2. Am Mineral 76(9–10):1769–1772

    Google Scholar 

  • Shinoda K, Yamakata M, Nanba T, Kimura H, Moriwaki T, Kondo Y, Kawamoto T, Niimi N, Miyoshi N, Aikawa N (2002) High-pressure phase transition and behavior of protons in brucite Mg(OH)2: a high-pressure-temperature study using IR synchrotron radiation. Phys Chem Mineral 29(6):396–402

    Article  Google Scholar 

  • Varga T, Wilkinson AP, Angel RJ (2003) Fluorinert as a pressure-transmitting medium for high-pressure diffraction studies. Rev Sci Instrum 74(10):4564–4566

    Article  Google Scholar 

  • Xia X, Weidner DJ, Zhao H (1998) Equation of state of brucite: single-crystal Brillouin spectroscopy study and polycrystalline pressure-volume-temperature measurement. Am Mineral 83(1–2):68–74

    Google Scholar 

Download references

Acknowledgments

We thank journal reviewers (Dr. Reynard and anonymous) for their useful comments, and Dr. Angel for his suggestions in the EOS-FIT program. The WAND is operated jointly by the Japan Atomic Energy Agency and ORNL as part of the US–Japan Cooperative Program on Neutron Scattering. This research was sponsored by the ORNL Laboratory Directed Research and Development Program, and by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy under contract DE-AC05-00OR22725, Oak Ridge National Laboratory, managed by UT-Battle, LLC.

Author information

Authors and Affiliations

  1. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831-6110, USA

    Juske Horita

  2. Neutron Scattering Science Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831-6110, USA

    António M. dos Santos, Christopher A. Tulk & Bryan C. Chakoumakos

  3. Institute of Experimental Mineralogy, Russian Academy of Science, Moscow, Russia

    Veniamin B. Polyakov

Authors
  1. Juske Horita
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. António M. dos Santos
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Christopher A. Tulk
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bryan C. Chakoumakos
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Veniamin B. Polyakov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Juske Horita.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Horita, J., dos Santos, A.M., Tulk, C.A. et al. High-pressure neutron diffraction study on H–D isotope effects in brucite. Phys Chem Minerals 37, 741–749 (2010). https://doi.org/10.1007/s00269-010-0372-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00269-010-0372-5

Keywords

Search

Navigation