Reduced radiative conductivity of low spin FeO6-octahedra in FeCO3 at high pressure and temperature

Abstract

The ability of Earth's mantle to conduct heat by radiation is determined by optical properties of mantle phases. Optical properties of mantle minerals at high pressure are accessible through diamond anvil cell experiments, but because of the intense thermal radiation at T>1000 K such studies are limited to lower temperatures. Accordingly, radiative thermal conductivity at mantle conditions has been evaluated with the assumption of the temperature-independent optical properties. Particularly uncertain is the temperature-dependence of optical properties of lower mantle minerals across the spin transition, as the spin state itself is a strong function of temperature. Here we use laser-heated diamond anvil cells combined with a pulsed ultra-bright supercontinuum laser probe and a synchronized time-gated detector to examine optical properties of high and low spin ferrous iron at 45–73 GPa up to 1600 K in an octahedral crystallographic unit (FeO6), one of the most abundant building blocks in the mantle. Siderite (FeCO3) is used as a model for FeO6-octahedra as it contains no ferric iron and exhibits a sharp optically apparent pressure-induced spin transition at 44 GPa, simplifying data interpretation. We find that the optical absorbance of low spin FeO6 increases with temperature due to the partially lifted Laporte selection rule. The temperature-induced low-to-high spin transition, however, results in a dramatic drop in absorbance of the FeO6 unit in siderite. The absorption edge (Fe–O charge transfer) red-shifts (∼1 cm−1/K) with increasing temperature and at T>1600 K and P>70 GPa becomes the dominant absorption mechanism in the visible range, suggesting its superior role in reducing the ability of mantle minerals to conduct heat by radiation. This implies that the radiative thermal conductivity of analogous FeO6-bearing minerals such as ferropericlase, the second most abundant mineral in the Earth's lower mantle, is substantially reduced approaching the core–mantle boundary conditions.