High-pressure phases of Co2GeO4, Ni2GeO4, Mn2GeO4 and MnGeO3: implications for the germanate-silicate modeling scheme and the Earth's mantle

In a diamond-anvil press coupled with YAG laser heating, the spinels of Co₂GeO₄ and Ni₂GeO₄ have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO₃ transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a₀ = 5.084 ± 0.002, b₀ = 5.214 ± 0.002, and c₀ = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO₃ is ?6.6%. Mn₂GeO₄ disproportionates into a mixture of the perovskite phase of MnGeO₃ plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.     

A M?ssbauer effect study of Fe3+ bearing γ-Fe2SiO4

Three synthetic Fe³⁺ bearing λ-Fe₂SiO₄ were analyzed using electron probe method, and the M?ssbauer spectra of the samples at 298 K, 150 K, and 95 K were measured. Each spectrum at three temperatures is composed of two doublets. These two doublets are assigned to Fe²⁺ in the octahedral sites and Fe³⁺ in the tetrahedral sites, respectively. Site occupancies were determined. The results show that Fe³⁺ and a small amount of Si⁴⁺ are in the tetrahedral and octahedral sites, respectively. The average bond lengths of the octahedral and tetrahedral sites were calculated according to the equations primarily given by Hill et al., O’Neill and Navrotsky and modified by the authors. Furthermore, the octahedral and tetrahedral bond lengths were used to calculate cell parameters and oxygen parameters. In addition, Fe³⁺ line broadening in the M?ssbauer spectra of Fe³⁺ bearing λ-Fe₂SiO₄ were interpreted by using the next nearest neighbor effects