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H2O storage capacity of MgSiO3 clinoenstatite at 8–13 GPa, 1,100–1,400°C

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Abstract

We present H2O analyses of MgSiO3 pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C. Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals were high clinoenstatite (C2/c) during conditions of synthesis. H2O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy on randomly oriented crystals. Measured H2O concentrations increase with pressure and range from 0.08 wt.% H2O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H2O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend, which we attribute to diminishing activity of H2O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure. We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H2O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H2O partitioning between olivine and clinoenstatite gives values of D ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D wd/CEn, gives a value of 2.8 ± 0.4.

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Acknowledgments

We gratefully acknowledge the assistance of Cyril Aubaud, and Yunbin Guan during SIMS analyses at ASU and of Jinping Dong for help with the Raman spectrometer and Ellery Frahm for help with the electron microprobe. We thank Steve Jacobsen for illuminating discussions, and two anonymous reviewers for their thoughtful comments and suggestions. Parts of this work were carried out in the Minnesota Characterization Facility, which receives partial support from NSF through the NNIN program. This work supported by NSF EAR0456405.

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  1. Department of Geology and Geophysics, University of Minnesota, 108 Pillsbury Hall, Minneapolis, MN, 55455, USA

    A. C. Withers & M. M. Hirschmann

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  1. A. C. Withers
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Correspondence to A. C. Withers.

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Communicated by T.L. Grove.

Appendix 1: Multi-anvil pressure calibration

Appendix 1: Multi-anvil pressure calibration

The 14–8 assembly was calibrated against the Bi I–II and III–V transitions at 25°C (Piermarini and Block 1975), by reversal of the coesite-stishovite phase transformation at 1,200°C (Zhang et al. 1993) and using a high pressure fixed point defined by coexisting (Mg,Fe)2SiO4 phases at 1,400°C (Fig. 9). An additional constraint was provided by a half-bracket of the Mg2SiO4 olivine-wadsleyite phase transition at 1,200°C (Morishima et al. 1994). Following the technique described by Frost and Dolejš (2007), the high pressure fixed point was determined by analysis of coexisting phases in the (Mg,Fe)2SiO4 phase diagram. Starting materials were constructed from mixtures of dried reagent MgO, crystalline SiO2, FeO and Fe metal such that each composition would form an assemblage of olivine polymorph(s), magnesiowüstite and ∼10% metallic iron under the experimental conditions. Bulk Fe/(Fe + Mg) ratios were varied so as to maximise the likelihood of producing coexisting phases of (Mg,Fe)2SiO4 in the charge. The four starting compositions were loaded into a four-chambered Al2O3 capsule, as described in Frost and Dolejš (2007), and the alumina capsule was wrapped in Fe foil and positioned immediately below the thermocouple junction in the 14–8 assembly. The starting materials and assembled octahedron were stored under vacuum prior to running the calibration experiment. The experiment was pressurised and heated at 1,400°C for 8 h before turning off the power supply and depressurising to ambient conditions. The capsule was recovered, sectioned with a wire saw in a plane perpendicular to the axis of the heater and prepared for electron microprobe analysis (Fig. 10, inset). The exposed areas of the capsule chambers were located within 0.3 mm of the thermocouple junction at the end of the experiment. A 20 μm rim of garnet formed at the outer edge of each chamber through reaction with the Al2O3 capsule, and metallic Fe was dispersed throughout the interior of each chamber. The compositions and Fe# for coexisting (Mg,Fe)2SiO4 polymorphs and magnesiowüstite determined by electron microprobe are given in Table 3, and the compositions of (Mg,Fe)2SiO4 polymorphs are plotted as a function of Fe# at a pressure that best matches the (Mg,Fe)2SiO4 phase diagram in Fig. 10. The uncertainty in pressure determination for this fixed point, based on the fit to the phase diagram, is estimated to be ±0.05 GPa, and the uncertainty in pressure determination using the calibration curve (Fig. 9) is estimated to be ±0.5 GPa.

Fig. 9
figure 9

Force-pressure relationship for the 14–8 assembly. The square symbols represent fixed points, and each triangle demarcates a pressure constraint provided by phase stability

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Fig. 10
figure 10

Phase diagram for (Mg,Fe)2SiO4 calculated by Frost and Dolejš (2007) using the data of Frost (2003) and Jacobs and Oonk (2001). The Fe# (Fe/(Fe + Mg)) of (Mg,Fe)2SiO4 polymorphs present in each of the four chambers of the Al2O3 capsule (labelled A-D in the inset backscattered electron image) are plotted as circles at a pressure that best matches the phase diagram. Coexisting mineral pairs within a chamber are connected by dotted lines

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Table 3 Phase compositions determined by electron microprobe
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Withers, A.C., Hirschmann, M.M. H2O storage capacity of MgSiO3 clinoenstatite at 8–13 GPa, 1,100–1,400°C. Contrib Mineral Petrol 154, 663–674 (2007). https://doi.org/10.1007/s00410-007-0215-7

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