Abstract
Hydrogen transport from the surface to the deep interior and distribution in the mantle are important in the evolution and dynamics of the Earth. An aluminum oxy-hydroxide, δ-AlOOH, might influence hydrogen transport in the deep mantle because of its high stability extending to lower mantle conditions. The compressional behavior and spin states of δ-(Al,Fe3+)OOH phases were investigated with synchrotron X-ray diffraction and Mössbauer spectroscopy under high pressure and room temperature. Pressure-volume (P-V) profiles of the δ-(Al0.908(9)57Fe0.045(1))OOH1.14(3) [Fe/(Al+Fe) = 0.047(10), δ-Fe5] and the δ-(Al0.832(5)57Fe0.117(1))OOH1.15(3) [Fe/(Al+Fe) = 0.123(2), δ-Fe12] show that these hydrous phases undergo two distinct structural transitions involving changes in hydrogen bonding environments and a high- to low-spin crossover in Fe3+. A change of axial compressibility accompanied by a transition from an ordered (P21nm) to disordered hydrogen bond (Pnnm) occurs near 10 GPa for both δ-Fe5 and δ-Fe12 samples. Through this transition, the crystallographic a and b axes become stiffer, whereas the c axis does not show such a change, as observed in pure δ-AlOOH. A volume collapse due to a transition from high- to low-spin states in the Fe3+ ions is complete below 32–40 GPa in δ-Fe5 and δ-Fe12, which i ~10 GPa lower than that reported for pure ε-FeOOH. Evaluation of the Mössbauer spectra of δ-(Al0.824(10)57Fe0.126(4))OOH1.15(4) [Fe/(Al+Fe) = 0.133(3), δ-Fe13] also indicate a spin transition between 32–45 GPa. Phases in the δ-(Al,Fe)OOH solid solution with similar iron concentrations as those studied here could cause an anomalously high ρ/νΦ ratio (bulk sound velocity, defined as at depths corresponding to the spin crossover region (~900 to ~1000 km depth), whereas outside the spin crossover region a low ρ/νΦ anomaly would be expected. These results suggest that the δ-(Al,Fe)OOH solid solution may play an important role in understanding the heterogeneous structure of the deep Earth.
