Controls on lithium concentration and diffusion in zircon

Thermal annealing of zircons prior to uranium-lead dating by laser ablation inductively coupled plasma mass spectrometry is a commonly-implemented procedure which improves data accuracy and precision by partially repairing radiation damage from the decay of uranium and thorium. However, it also leads to significantly higher concentrations of lithium in the zircon lattice, which become positively correlated with trivalent yttrium and rare earth elements. Prior to such treatments, zircons typically contain lithium below detection limits (typically <0.55 μg g⁻¹), unless correlated with lanthanum and aluminum (i.e., melt/mineral inclusion tracer elements). This suggests that lithium in zircon is primarily sequestered within inclusions, and is able to permeate the crystal lattice to couple with yttrium and rare earth elements during the thermal annealing procedure. This process occurs 2–3 orders of magnitude faster than diffusion experiments have previously determined, indicating that another diffusion mechanism may apply. A model is proposed, whereby: (i) charge compensation of stoichiometrically over-abundant trivalent cations under water-rich magmatic conditions is likely accomplished by hydrogen, given the incompatibility of lithium in zircon and the abundance of hydrogen. However, (ii) conditions that are high temperature and low pressure (characteristic of both thermal annealing and the syn-eruptive environment), drive silicate melt inclusions to exsolve water, generating a motive force for both hydrogen and lithium from inclusions to permeate the lattice in order to reestablish electrochemical equilibrium between the interior and exterior of the zircon. To test the pressure dependency of lithium migration in the zircon lattice, thermal annealing experiments were performed at 850 °C and 1 bar, 2 kbar and 6 kbar using zircons from the Fish Canyon Tuff. The experiments demonstrate that thermal annealing at 2 and 6 kbar inhibits lithium mobility, with zircons registering lithium concentrations below detection limits similar to controls. The experimental results suggest that lithium concentrations in zircon are vulnerable to rapid perturbation by decompression (concurrent with high temperatures), which further indicate that lithium-in-zircon diffusion data should be interpreted with caution.