Diffusive Fractionation of Lithium Isotopes in Olivine

Abstract:

Systematic lithium isotope variations along concentration gradients found in olivine and pyroxene grains from terrestrial, lunar and martian rocks have been attributed to diffusive isotopic fractionation [Beck et al., 2006; Tang et al., 2007]. In some cases, these isotopic excursions are so large that a single grain may display isotopic variability that spans almost the entire range of documented terrestrial values [Jeffcoate et al., 2007]. In this study, we present the results of experiments to examine diffusive isotopic fractionation of lithium in olivine. The experiments comprised crystallographically oriented slabs of San Carlos olivine juxtaposed with either spodumene powder or a lithium rich pyroxene crystal. Experiments were conducted at 1 GPa and 0.1MPa over a temperature range of 1000 to 1125⁰C. Oxygen fugacity in the 0.1MPa experiments was controlled using the wustite-magnetite and nickel-nickel oxide solid buffer assemblages. Lithium concentrations generally decrease smoothly away from the edges of the grains; however, experiments involving diffusion parallel to the a-axis consistently show peculiar wavy or segmented concentration profiles. Lithium diffusivity parallel to the c-axis is on the order of 1E-14m²/s at 1100⁰C. The diffusivity parallel to the c-axis is more than an order of magnitude faster than diffusion parallel to the b-axis and correlates positively with oxygen fugacity. The lithium isotopic composition, δ⁷Li = 1000‰ * ((δ⁷Li_sample- δ⁷Li_{grain center})/ δ⁷Li_{grain center}), shows a decrease away from the edge of the grain to a minimum value (up to 70‰ lighter) and then an abrupt increase back to the initial isotopic composition of the olivine grain. This isotopic profile is similar to those found in natural grains and an experimental study on diffusive fractionation of lithium isotopes in pyroxene [Richter et al., 2014]. Results from the present study are modeled using the approach of Dohmen et al. [2010], which assumes lithium diffusion occurs on both a metal and interstitial site and that lithium is able to jump between these two sites. The best fits to the results show that diffusive isotopic fractionation may occur on both the interstitial and metal site but the degree of diffusive isotopic fractionation is always greater on the interstitial site.