Pressure–induced crystallization of biogenic hydrous amorphous silica

Abstract

Samples of the diatom Nitzschia cf. frustulum, collected from Lake Yogo, Siga Prefecture, Japan, were cultured in the laboratory. Organic components of the diatom cell were removed by washing with acetone and sodium hypochlorite. The remaining frustules were studied by scanning electron microscopy coupled with energy dispersive X–ray spectroscopy (SEM–EDX), Fourier–transform infrared (FTIR) spectroscopy, and synchrotron X–ray diffraction. The results showed that the spindle–shaped diatom frustule was composed of hydrous amorphous silica. Pressure–induced phase transformation of the diatom frustule was investigated by in situ Raman spectroscopic analysis. With exposure to 0.3 GPa at 100 °C, the Raman band corresponding to quartz occurred at ν = 465 cm⁻¹. In addition, a characteristic Raman band for moganite was observed at 501 cm⁻¹. From the integral ratio of Raman bands, the moganite content in the probed area was estimated to be approximately 50 wt%. With increased pressure and temperature, the initial morphology of diatom frustules was totally changed to a characteristic spherical particle with a diameter of about 2 µm. Increasing pressure to 5.7 GPa at 100 °C resulted in the appearance of a Raman band assignable to coesite at 538 cm⁻¹. That is, with compression and heating, hydrous amorphous silica can be readily crystallized into quartz, moganite, and coesite. First–principles calculations revealed that a disiloxane molecule with a trans configuration is twisted 60° with a close approach of a water molecule, which leads to a trans to cis configuration change. It is therefore reasonable to assume that during crystallization of hydrous amorphous silica, an Si–O–Si bridging unit with the cis configuration would survive as a structural defect, and could subsequently crystallize into moganite by maintaining that geometry. This hypothesis is adaptable to the phase transformation from hydrous amorphous silica to coesite as well, because coesite has four–membered rings and is easily formed from hydrous amorphous silica under high pressure and temperature conditions.