Compressibility and thermal expansion of hydrous ringwoodite with 2.5(3) wt% H2O

Ringwoodite ( -Mg2SiO4) is the stable polymorph of olivine in the transition zone between 525–660 km depth, and can incorporate weight percent amounts of H2O as hydroxyl, with charge compensated mainly by Mg vacancies (Mg2+ = 2H+), but also possibly as (Si4+ = 4H+ and Mg2+ + 2H+ = Si4+). We synthesized pure Mg ringwoodite containing 2.5(3) wt% H2O, 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 KT0 = 159(7) GPa and (dKT/dP)P = 0 = K' = 6.7(7) for single-crystal XRD; KT0 = 161(4) GPa and K' = 5.4(6) for powder XRD, with KT0 = 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 V0 of 40(4) 10 6/K (143–736 K), and 29(2) 10 6/K (143–586 K before irreversible expansion). V(Mg) have 0 values of 41(3) 10 6/K (143–736 K), and V(Si) has 0 values of 20(3) 10 6/K (143–586 K) and 132(4) 10 6K (586–736 K). Based on the experimental data and previous work from 29Si NMR, we propose that during the irreversible expansion, a small amount of H+ cations in Mg sites transfer to Si sites without changing the cubic spinel structure of ringwoodite, and the substituted Si4+ 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 Mg2+ = 2H+ dominates up to about 2 wt% H2O, where a discontinuity in the volume vs. H2O content trend suggests that other hydration mechanisms become important at very high H2O contents.