Abstract
Recent experiments have demonstrated the existence of previously unknown iron oxides at high pressure and temperature including newly discovered pyrite-type FeO(2) and FeO(2)H(x) phases stable at deep terrestrial lower mantle pressures and temperatures. In the present study, we probed the iron oxidation state in high-pressure transformation products of Fe(3+)OOH goethite by in situ X-ray absorption spectroscopy in laser-heated diamond-anvil cell. At pressures and temperatures of ~91 GPa and 1,500-2,350 K, respectively, that is, in the previously reported stability field of FeO(2)H(x), a measured shift of -3.3 ± 0.1 eV of the Fe K-edge demonstrates that iron has turned from Fe(3+) to Fe(2+). We interpret this reductive valence change of iron by a concomitant oxidation of oxygen atoms from O(2-) to O(-), in agreement with previous suggestions based on the structures of pyrite-type FeO(2) and FeO(2)H(x) phases. Such peculiar chemistry could drastically change our view of crystal chemistry in deep planetary interiors.