Low Fe3+ in Bridgmanite and Possible Existence of an Oxidizing Layer in the Mid Mantle

Monday, 14 December 2015: 16:45
301 (Moscone South)
Sang-Heon Dan Shim1, Brent Grocholski2, Yu Ye3, Ercan E. Alp4, Shenzhen Xu5, Dane Morgan5, Yue Meng6 and Vitali Prakapenka4, (1)Arizona State University, School of Earth and Space Exploration, Tempe, AZ, United States, (2)Smithsonian Institution, Washington, DC, United States, (3)China University of Geosciences Wuhan, Wuhan, China, (4)University of Chicago, Argonne, IL, United States, (5)Univ of Wisconsin- Madison, Madison, WI, United States, (6)Carnegie Institution of Washington, HPCAT, Argonne, IL, United States
Earlier multi-anvil experiments suggested a large amount of Fe3+ (60-70%) in bridgmanite (Bm) through charge disproportionation of Fe2+ to Fe3+ and metallic iron at the pressure-temperature (P-T) conditions of the topmost lower mantle (<25 GPa). Similar amount of Fe3+ has been recently documented at higher pressures but without redox control. If metallic iron can be stabilized, the lower mantle will have very low oxygen fugacity. However, the inclusions in lower-mantle diamonds suggest large variations in oxygen fugacity to much more oxidizing conditions. We mixed (Mg0.75Fe0.2Al0.05)(Al0.05Si0.95)O3 starting materials with 2-5 wt% metallic iron, in order to ensure reducing conditions during the synthesis of Bm in the laser-heated diamond-anvil cell. X-ray diffraction and Mossbauer spectroscopy were performed at APS. The recovered samples were analyzed using energy dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) at ASU. We found that 60-70% of iron is Fe3+ in Bm at P<40 GPa and P>70 GPa, consistent with previous studies. However, Bm synthesized at 40-70 GPa contains very little Fe3+ (~10%), indicating that charge disproportionation does not occur at depths between 1000 and 1700 km in the lower mantle. The low metallic iron layer (LMIL) can be oxidized in early Earth, because of unbalanced Fe3+ and metallic iron in lower-mantle flow by core formation. The oxidizing nature of the layer may impact the siderophile element partitioning between metal and silicates if magma ocean was sufficiently deep. The layer can be further oxidized through solid mantle convection because of injection of oxidizing surface materials. The elevated oxygen fugacity will potentially make LMIL a distinct geochemical reservoir. Due to oxidizing conditions, carbon will form diamond instead of FeC in the layer. Strong partitioning of Fe2+ into ferropericlase (Fp) and the low content of Fe3+ in Bm will enrich Fp with iron (Fe2+) in LMIL. Because the Fe3+ content changes gradually, the upper and lower boundaries of the layer would not produce seismically detectable discontinuities. The layer may have low thermal conductivity due to the low Fe3+ content in Bm, possibly affecting dynamics of the mid mantle.