An eruption chronometer based on experimentally determined H-Li and H-Na diffusion in quartz applied to the Bishop Tuff

Abstract The diffusion of hydrogen in natural hydrothermal quartz crystals was studied between 657–956 °C at atmospheric pressure and various oxygen fugacity ( f O 2 ) conditions. Single crystals of OH-bearing quartz were dehydrated in the presence of Li or Na-enriched powders to induce Li-H or Na-H exchange, with the resulting diffusion profiles measured by both Fourier transform infrared (FTIR) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Diffusion parallel to [0001], i.e. the crystallographic c-axis, is described by: log 10 ⁡ D ( m 2 s − 1 ) = − 6.5 ± 0.3 + − 100.4 ± 5.2 kJ mol − 1 2.303 RT where log10D is the base 10 logarithm of the diffusion coefficient, R is the gas constant and T is the temperature in kelvins, and uncertainties are 1 σ. Diffusion is not affected by ( f O 2 ) in this system. Diffusion perpendicular to [0001] is consistently slower, but quantitative constraints cannot be obtained from our data given experimental limitations. This diffusivity is primarily associated with H+-Li+ (or H+-Na+, Na+-Li+) exchange, where the H+ and Li+ are charge-balanced by tetrahedrally-coordinated Al3+. A faster mechanism may also exist where the monovalent cations are charge balanced by excess oxygen. The final defect population, as imaged by FTIR spectroscopy and LA-ICP-MS, likely results from a combination of diffusion and inter-site rearrangement of the monovalent cations. Regardless of such complexities, the determined Arrhenius relationship should be applicable for natural volcanic quartz crystals from the Bishop Tuff, California, wherein H+ is associated with Al3+, and H loss from quartz preceding and/or accompanying the eruption is charge-balanced by Li-gain, without Al movement. Li and H profiles from an example quartz crystal suggest that it experienced eruption/cooling timescales of just 16 minutes to 2.4 hours, showing the considerable promise of using frozen H diffusion profiles in quartz to extract timescales and thus elucidate the last moments of such explosive silicic eruptions.