Stability of Pure Hydrous Silica at Geotherm Temperatures up to 70 GPa

Abstract:

Stishovite, in the rutile structure with octahedrally coordinated silicon, is expected to exist in silica rich parts of subducted oceanic slabs and crustal fragments in the Earth’s mantle, and has been considered for a long time to be essentially anhydrous. However, Spektor et al., (2011) have shown that ~1.3 wt% can be incorporated into pure Al-free stishovite at 10 GPa and 723 K. Yet, the stability and physical properties of hydrous silica at mantle related pressures and temperatures are unknown.

We have synthesized hydrous silica samples in the multi anvil press at 9-20 GPa and 700-900 K, and in the laser-heated diamond anvil cell at 17-70 GPa and 1400-2100 K. Three different sample setups have been used: dry silica gel in an H₂O medium, anhydrous stishovite in an H₂O medium, and hydrous silica gel in a Ne or Ar medium.

The presence of percent level of water was found by Secondary Ion Mass Spectrometry, and Raman and Infrared spectroscopy measurements. X-ray diffraction patterns show that the unit-cell volumes of the recovered stishovite samples are greater by 0.2-3.9 % compared with anhydrous stishovite at 1 bar. The unit-cell volumes show strong linear correlation with their c/a ratio suggesting that the same OH substitution mechanism persists for a wide range of water content. Based on unit-cell volumes vs water content calibration by Spektor et al., (2011), our samples contain 0.3-7.9 wt% H₂O. We found that pure silica is capable of containing as much as 4.9 wt% of H₂O at temperatures close to those of the mantle geotherm (e.g., sample synthesized at ~1997 K and ~67 GPa). The highest water contents were found at the highest pressures, suggesting that the pressure stabilizes OH in dense silica.

X-ray diffraction patterns have also shown several new diffraction lines upon compression and heating which appear from 45 GPa (1500-2100 K) and are observed up to 100 GPa. The peaks appear to belong to a new hydrous silica phase stable at higher pressures and temperatures. The high solubility of water in SiO₂ at the mantle geotherm temperatures at higher pressures will change our understanding of the stability of free silica and of the deep water transport in the Earth’s mantle.