• journal_title：American Mineralogist
• Contributor：Yu Ye ; David A. Brown ; Joseph R. Smyth ; Wendy R. Panero ; Steven D. Jacobsen ; Yun-Yuan Chang ; Joshua P. Townsend ; Sylvia-Monique Thomas ; Erik H. Hauri ; Przemyslaw Dera ; Daniel J. Frost
• Publisher：Mineralogical Society of America
• Date：2012-
• Format：text/html
• Language：en
• Identifier：10.2138/am.2012.4010
• journal_abbrev：American Mineralogist
• issn：0003-004X
• volume：97
• issue：4
• firstpage：573
• section：Articles

Ringwoodite (γ-Mg<sub>2sub>SiO<sub>4sub>) is the stable polymorph of olivine in the transition zone between 525–660 km depth, and can incorporate weight percent amounts of H<sub>2sub>O as hydroxyl, with charge compensated mainly by Mg vacancies (Mg<sup>2+sup> = 2H<sup>+sup>), but also possibly as (Si<sup>4+sup> = 4H<sup>+sup> and Mg<sup>2+sup> + 2H<sup>+sup> = Si<sup>4+sup>). We synthesized pure Mg ringwoodite containing 2.5(3) wt% H<sub>2sub>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 and 740 K at room pressure. A third-order Birch-Murnaghan equation of state (BM3 EOS) fits values of the isothermal bulk modulus K<sub>T0sub> = 159(7) GPa and (dK<sub>Tsub>/dP)<sub>Psub> <sub>= 0sub> = K′ = 6.7(7) for single-crystal XRD; K<sub>T0sub> = 161(4) GPa and K′ = 5.4(6) for powder XRD, with K<sub>T0sub> = 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 α<sub>Vsub><sub>0sub> of 40(4) ×10<sup>−6sup>/K (143–736 K), and 29(2) ×10<sup>−6sup>/K (143–586 K before irreversible expansion). V(Mg) have α<sub>0sub> values of 41(3) ×10<sup>−6sup>/K (143–736 K), and V(Si) has α<sub>0sub> values of 20(3) ×10<sup>−6sup>/K (143–586 K) and 132(4) ×10<sup>−6sup>K (586–736 K). Based on the experimental data and previous work from <sup>29sup>Si NMR, we propose that during the irreversible expansion, a small amount of H<sup>+sup> cations in Mg sites transfer to Si sites without changing the cubic spinel structure of ringwoodite, and the substituted Si<sup>4+sup> cations move to the normally vacant octahedral site at (½, ½, 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+sup> = 2H<sup>+sup> dominates up to about 2 wt% H<sub>2sub>O, where a discontinuity in the volume vs. H<sub>2sub>O content trend suggests that other hydration mechanisms become important at very high H<sub>2sub>O contents.