skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Quantification of water in hydrous ringwoodite

Abstract

Here, ringwoodite, γ-(Mg,Fe) 2SiO 4, in the lower 150 km of Earth’s mantle transition zone (410-660 km depth) can incorporate up to 1.5-2 wt% H 2O as hydroxyl defects. We present a mineral-specific IR calibration for the absolute water content in hydrous ringwoodite by combining results from Raman spectroscopy, secondary ion mass spectrometery (SIMS) and proton-proton (pp)-scattering on a suite of synthetic Mg- and Fe-bearing hydrous ringwoodites. H 2O concentrations in the crystals studied here range from 0.46 to 1.7 wt% H 2O (absolute methods), with the maximum H 2O in the same sample giving 2.5 wt% by SIMS calibration. Anchoring our spectroscopic results to absolute H-atom concentrations from pp-scattering measurements, we report frequency-dependent integrated IR-absorption coefficients for water in ringwoodite ranging from 78180 to 158880 L mol -1cm -2, depending upon frequency of the OH absorption. We further report a linear wavenumber IR calibration for H 2O quantification in hydrous ringwoodite across the Mg 2SiO 4-Fe 2SiO 4 solid solution, which will lead to more accurate estimations of the water content in both laboratory-grown and naturally occurring ringwoodites. Re-evaluation of the IR spectrum for a natural hydrous ringwoodite inclusion in diamond from the study of the crystal contains 1.43more » ± 0.27 wt% H 2O, thus confirming near-maximum amounts of H 2O for this sample from the transition zone.« less

Authors:
 [1];  [2];  [2];  [3];  [3];  [4];  [5];  [6];  [3]
  1. Univ. of Nevada, Las Vegas, NV (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Univ. de Bundeswehr Munchen, Neubiberg (Germany)
  4. Carnegie Inst. of Washington, Washington, D.C. (United States)
  5. Helmholtz-Zentrum Potsdam, Deutsches GeoForschungsZentrum (GFZ), Potsdam (Germany)
  6. Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
Carnegie Inst. of Washington, Washington, DC (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1335510
Grant/Contract Number:
NA0002006; EAR-1215957; EAR-0748707
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Frontiers in Earth Science
Additional Journal Information:
Journal Volume: 2; Journal ID: ISSN 2296-6463
Publisher:
Frontiers Research Foundation
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; IR spectroscopy; water in nominally anhydrous minerals; transition zone; mineral-specific absorption coefficient; SIMS; Raman spectroscopy; proton-proton scattering; ringwoodite

Citation Formats

Thomas, Sylvia -Monique, Jacobsen, Steven D., Bina, Craig R., Reichart, Patrick, Moser, Marcus, Hauri, Erik H., Koch-Muller, Monika, Smyth, Joseph R., and Dollinger, Gunther. Quantification of water in hydrous ringwoodite. United States: N. p., 2015. Web. doi:10.3389/feart.2014.00038.
Thomas, Sylvia -Monique, Jacobsen, Steven D., Bina, Craig R., Reichart, Patrick, Moser, Marcus, Hauri, Erik H., Koch-Muller, Monika, Smyth, Joseph R., & Dollinger, Gunther. Quantification of water in hydrous ringwoodite. United States. doi:10.3389/feart.2014.00038.
Thomas, Sylvia -Monique, Jacobsen, Steven D., Bina, Craig R., Reichart, Patrick, Moser, Marcus, Hauri, Erik H., Koch-Muller, Monika, Smyth, Joseph R., and Dollinger, Gunther. Wed . "Quantification of water in hydrous ringwoodite". United States. doi:10.3389/feart.2014.00038. https://www.osti.gov/servlets/purl/1335510.
@article{osti_1335510,
title = {Quantification of water in hydrous ringwoodite},
author = {Thomas, Sylvia -Monique and Jacobsen, Steven D. and Bina, Craig R. and Reichart, Patrick and Moser, Marcus and Hauri, Erik H. and Koch-Muller, Monika and Smyth, Joseph R. and Dollinger, Gunther},
abstractNote = {Here, ringwoodite, γ-(Mg,Fe)2SiO4, in the lower 150 km of Earth’s mantle transition zone (410-660 km depth) can incorporate up to 1.5-2 wt% H2O as hydroxyl defects. We present a mineral-specific IR calibration for the absolute water content in hydrous ringwoodite by combining results from Raman spectroscopy, secondary ion mass spectrometery (SIMS) and proton-proton (pp)-scattering on a suite of synthetic Mg- and Fe-bearing hydrous ringwoodites. H2O concentrations in the crystals studied here range from 0.46 to 1.7 wt% H2O (absolute methods), with the maximum H2O in the same sample giving 2.5 wt% by SIMS calibration. Anchoring our spectroscopic results to absolute H-atom concentrations from pp-scattering measurements, we report frequency-dependent integrated IR-absorption coefficients for water in ringwoodite ranging from 78180 to 158880 L mol-1cm-2, depending upon frequency of the OH absorption. We further report a linear wavenumber IR calibration for H2O quantification in hydrous ringwoodite across the Mg2SiO4-Fe2SiO4 solid solution, which will lead to more accurate estimations of the water content in both laboratory-grown and naturally occurring ringwoodites. Re-evaluation of the IR spectrum for a natural hydrous ringwoodite inclusion in diamond from the study of the crystal contains 1.43 ± 0.27 wt% H2O, thus confirming near-maximum amounts of H2O for this sample from the transition zone.},
doi = {10.3389/feart.2014.00038},
journal = {Frontiers in Earth Science},
number = ,
volume = 2,
place = {United States},
year = {Wed Jan 28 00:00:00 EST 2015},
month = {Wed Jan 28 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:
  • Review of recent mineral physics literature shows consistent trends for the influence of Fe and H 2O on the bulk modulus (K0) of wadsleyite and ringwoodite, the major phases of Earth's mantle transition zone (410–660 km). However, there is little consensus on the first pressure derivative, K0' = (dK/dP)P=0, which ranges from about 4 to >5 across experimental studies and compositions. Here we demonstrate the importance of K0' in evaluating the bulk sound velocity of the transition zone in terms of water content and provide new constraints on the effect of H 2O on K0' for wadsleyite and ringwoodite bymore » conducting a comparative compressibility study. In the experiment, multiple crystals of hydrous Fo90 wadsleyite containing 2.0 and 0.25 wt % H 2O were loaded into the same diamond anvil cell, along with hydrous ringwoodite containing 1.4 wt % H 2O. By measuring their pressure-volume evolution simultaneously up to 32 GPa, we constrain the difference in K0' independent of the pressure scale, finding that H 2O has no effect on K0', whereas the effect of H 2O on K0 is significant. The fitted K0' values of hydrous wadsleyite (0.25 and 2.0 wt % H 2O) and hydrous ringwoodite (1.4 wt % H 2O) examined in this study were found to be identical within uncertainty, with K0' ~3.7(2). New secondary-ion mass spectrometry measurements of the H 2O content of these and previously investigated wadsleyite samples shows the bulk modulus of wadsleyite is reduced by 7.0(5) GPa/wt % H 2O, independent of Fe content for upper mantle compositions. Because K0' is unaffected by H 2O, the reduction of bulk sound velocity in very hydrous regions of transition zone is expected to be on the order of 1.6%, which is potentially detectible in high-resolution, regional seismology studies.« less
  • Ringwoodite ({gamma}-Mg{sub 2}SiO{sub 4}) is the stable polymorph of olivine in the transition zone between 525-660 km depth, and can incorporate weight percent amounts of H{sub 2}O as hydroxyl, with charge compensated mainly by Mg vacancies (Mg{sup 2+} = 2H{sup +}), but also possibly as (Si{sup 4+} = 4H{sup +} and Mg{sup 2+} + 2H{sup +} = Si{sup 4+}). We synthesized pure Mg ringwoodite containing 2.5(3) wt% H{sub 2}O, measured by secondary ion mass spectrometry (SIMS), and determined its compressibility at 300 K by single-crystal and powder X-ray diffraction (XRD), as well as its thermal expansion behavior between 140 andmore » 740 K at room pressure. A third-order Birch-Murnaghan equation of state (BM3 EOS) fits values of the isothermal bulk modulus K{sub T0} = 159(7) GPa and (dK{sub T}/dP){sub P = 0} = K' = 6.7(7) for single-crystal XRD; K{sub T0} = 161(4) GPa and K' = 5.4(6) for powder XRD, with K{sub T0} = 160(2) GPa and K' = 6.2(3) for the combined data sets. At room pressure, hydrous ringwoodite breaks down by an irreversible unit-cell expansion above 586 K, which may be related to dehydration and changes in the disorder mechanisms. Single-crystal intensity data were collected at various temperatures up to 736 K, and show that the cell volume V(cell) has a mean thermal expansion coefficient {alpha}{sub V0} of 40(4) x 10{sup -6}/K (143-736 K), and 29(2) x 10{sup -6}/K (143-586 K before irreversible expansion). V(Mg) have {alpha}{sub 0} values of 41(3) x 10{sup -6}/K (143-736 K), and V(Si) has {alpha}{sub 0} values of 20(3) x 10{sup -6}/K (143-586 K) and 132(4) x 10{sup -6}K (586-736 K). Based on the experimental data and previous work from {sup 29}Si NMR, we propose that during the irreversible expansion, a small amount of H{sup +} cations in Mg sites transfer to Si sites without changing the cubic spinel structure of ringwoodite, and the substituted Si{sup 4+} cations move to the normally vacant octahedral site at (1/2, 1/2, 0). Including new SIMS data on this and several Mg-ringwoodite samples from previous studies, we summarize volume-hydration data and show that the Mg{sup 2+} = 2H{sup +} dominates up to about 2 wt% H{sub 2}O, where a discontinuity in the volume vs. H{sub 2}O content trend suggests that other hydration mechanisms become important at very high H{sub 2}O contents.« less
  • To understand the effect of hydration on the sound velocities of major mantle minerals and to constrain the mantle's H{sub 2}O budget, we have measured the single-crystal elastic moduli of hydrous ringwoodite, (Mg{sub 1.633}Fe{sub 0.231}{sup 2+}Fe{sub 0.026}{sup 3+})Si{sub 1.00}H{sub 0.179}O{sub 4} with 1.1 wt.% H{sub 2}O using Brillouin scattering combined with X-ray diffraction in an externally-heated diamond anvil cell up to 16 GPa and 673 K. Up to 12 GPa at 300 K, the presence of 1.1 wt.% H{sub 2}O lowers the elastic moduli of ringwoodite by 5-9%, but does not affect the pressure derivatives of the elastic moduli comparedmore » to anhydrous ringwoodite. The reduction caused by hydration is significantly enhanced when temperatures are elevated at high pressures. At 12 GPa, increasing temperature by {Delta}T = 100 K leads to a 1.3-2.4% reduction in the elastic moduli (C{sub 11}, C{sub 12}, and C{sub 14}). Comparing our results with seismic observations, we have evaluated the potential H{sub 2}O content in the lower part of the transition zone. Our results indicate that the observed seismic velocity anomalies and related depth depression of the 660-km discontinuity could be attributed to thermal variations together with the presence of {approx} 0.1 wt.% H{sub 2}O.« less