Dehydration of goethite during vacuum step-heating and implications for he retentivity characterization

Abstract

Uncertainty exists over what environmental conditions and mineralogical/chemical properties are required to ensure retention of helium such that (UTh)/He dates record the time of goethite crystallization. We undertook vacuum step heating experiments to determine He diffusion parameters for extrapolation to Earth surface conditions on 10 goethite specimens in which we had created a uniform distribution of 3He. Arrhenius plots of apparent diffusion coefficients on all samples follow the same pattern. At temperatures <200 °C the data define arrays consistent with progressive degassing of increasingly large crystallites. However, above 200 °C the computed diffusivities increase dramatically until about 80% of the helium is extracted, after which they suddenly decline. The sudden increase in diffusivity at 200 °C coincides with the onset of dehydration of the goethite structure, a process which continues throughout the remainder of the step heat. There is a strong correlation between evolved water and 3He amounts. These observations likely reflect previously reported processes of formation, growth, and coalescence of pores as the phase transition to hematite proceeds. While significantly higher dehydration temperatures of ∼270 °C are observed using techniques such as thermogravimetric analysis in air, the long step durations, and vacuum conditions of our experiments destabilize goethite. Orders of magnitude differences in the computed diffusivities among our samples may reflect crystallite-size-distribution control on dehydration kinetics, and the qualitative size distributions we infer from the step heats are consistent with SEM observations of crystallite lengths. Vacuum step-heating experiments in which goethite is decomposing cannot be used to determine He diffusion behavior in nature, but the inferred crystallite size distribution provides some useful indirect evidence. A strong relationship exists between metrics of the crystallite size distribution from step heating results and the degree of He retention in nature inferred from the 4He/3He method. This observation provides evidence supporting the validity of the 4He/3He technique for estimating retention, and further suggests that the dominant control on He retention in nature is the crystallite size distribution. Experiments under hydrothermal conditions in which goethite remains stable may be an alternative approach to address the question of He diffusion behavior in nature.