Li diffusion in zircon

Abstract

Diffusion of Li under anhydrous conditions at 1 atm and under fluid-present elevated pressure (1.0–1.2 GPa) conditions has been measured in natural zircon. The source of diffusant for 1-atm experiments was ground natural spodumene, which was sealed under vacuum in silica glass capsules with polished slabs of zircon. An experiment using a Dy-bearing source was also conducted to evaluate possible rate-limiting effects on Li diffusion of slow-diffusing REE+3 that might provide charge balance. Diffusion experiments performed in the presence of H2O–CO2 fluid were run in a piston–cylinder apparatus, using a source consisting of a powdered mixture of spodumene, quartz and zircon with oxalic acid added to produce H2O–CO2 fluid. Nuclear reaction analysis (NRA) with the resonant nuclear reaction 7Li(p,γ)8Be was used to measure diffusion profiles for the experiments. The following Arrhenius parameters were obtained for Li diffusion normal to the c-axis over the temperature range 703–1.151°C at 1 atm for experiments run with the spodumene source: $$ D_{\text{Li}} = 7.17 \times 10^{ - 7} { \exp }( - 275 \pm 11\,{\text{kJmol}}^{ - 1} /{\text{RT}}){\text{m}}^{2} {\text{s}}^{ - 1}.$$ Diffusivities are similar for transport parallel to the c-axis, indicating little anisotropy for Li diffusion in zircon. Similar Li diffusivities were also found for experiments run under fluid-present conditions and for the experiment run with the Dy-bearing source. Li diffusion is considerably faster than diffusion of other cations in zircon, with a smaller activation energy for diffusion. Although Li diffusion in zircon is comparatively rapid, zircons will be moderately retentive of Li signatures at mid-crustal metamorphic temperatures, but they are unlikely to retain this information for geologically significant times under high-grade metamorphism.