Abstract
The spin states of iron in deep magmas are one of the most important properties that affect the partitioning of iron between magmas and minerals and, thus, the gravitational stability of magmas in the Earth. We investigated the spin state and electronic environments of iron in a basaltic glass containing ~70 Fe3+/ΣFe at room temperature and pressures from 1 bar to 130 GPa using a diamond-anvil cell combined with energy domain synchrotron 57Fe Mössbauer source spectroscopy. The basaltic glass represents an analog of a multi-component magma typical for the Earth. The Mössbauer spectra could be fitted by a two pseudo-Voigt doublet model including a high quadrupole splitting (QS) doublet and a low QS doublet, which were assigned to high-spin Fe2+ and high-spin Fe3+, respectively. The high-spin states of Fe2+ and Fe3+ remained up to 130 GPa corresponding to the pressure in the lowermost mantle. The center shift values of high-spin Fe2+ and Fe3+ did not show large changes with pressure, ruling out sharp electronic changes in the basaltic glass. Therefore, a sharp and complete spin crossover of Fe2+ from the high-spin to the low-spin state does not appear to occur in the basaltic glass although the possibility of a partial spin transition cannot be fully excluded. The QS values of Fe2+ increased slightly at 0–20 GPa and above 100 GPa, and the higher value was preserved after decompression to ambient conditions. This behavior may be related to distortion of Fe2+ polyhedra due to short-range ordering on compression. Such a distortion of Fe2+ polyhedra could gradually stabilize Fe2+ in the basaltic glass with pressure compared to bridgmanite according to the Jahn-Teller effect, and thus could gradually enhance the partitioning of iron into deep magmas in the lower mantle.
Acknowledgments
Nanami Suzuki, Maki Hamada, Tatsuya Sakamaki, Akio Suzuki (Tohoku University), and Yasuo Ohishi (JASRI) contributed valuable discussion and technical support during the experiments. Bjorn Mysen (Carnegie Institution of Washington) and Clemens Prescher (University Cologne) provided valuable discussions and suggestions on the manuscript. This work was supported by the Grant-in-Aid for Scientific Research to E.O. (numbers 22000002 and 15H05748) from the Ministry of Education, Culture, Sports, Science, and Technology of the Japanese Government, and by the International Research and Training Group “Deep Earth Volatile Cycles” funded by the German Science Foundation (grant number GRK 2156/1). The synchrotron radiation experiments were performed at SPring-8 with the approval of the Japanese Radiation Research Institute (Proposals 2014A0104, 2014A3516, 2014B0104, 2014B3519, 2015A0104, and 2015B0104). F.M. was supported by the International Joint Graduate Program in Earth and Environmental Science (GP-EES), Tohoku University. This work and F.M. were supported by the JSPS Japanese-German Graduate Externship.
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