Revealing the radiation damage and Al-content impacts on He diffusion in goethite

Over the past few decades, the (U-Th)/He geochronological method on goethite has been more and more applied to date laterite formation and evolution or ore-deposit formation. However, questions remain on possible He loss by diffusion due to the polycrystalline structure of goethite and associated underestimation of the goethite crystallization date given by the (U-Th)/He age. Prior studies estimated helium loss in goethite to range from 2 to 30%, but no relation or models have been produced to explain such values. To clarify the situation, we firstly performed a complete review of experimental He diffusion data in natural goethite, that reveals the link between activation energy and He loss with the damage dose. To understand He diffusion behavior in goethite and model the He loss, natural defect and alpha damage as well as the chemical composition and growth structure effect on He diffusion have been investigated thanks to a multi-scale study. We used numerical simulations combining the Density Functional Theory (DFT) at the atomic scale and Kinetic Monte Carlo (KMC) simulations at the macroscopic scale. We found that He diffusion is purely anisotropic along the preferential elongated axis (i.e., b-axis) and He leaks out easily in defect-free goethite and Al-goethite. The consequence of this anisotropy is that crystallographic defects and alpha damage strongly lower the He diffusivity in goethite and Al-goethite by obstructing the diffusion channel or trapping He along the b-axis. Defect and damage impact on He diffusion is even larger for Al-goethite. The obtained He diffusion parameters for goethite containing defect and damage are similar to the activation energy and He diffusional loss obtained in natural goethite from the literature. We demonstrate the systematic dependence of the diffusion coefficient with damage dose and the impact of Al on He retention. He atoms are retained only at the favor of obstructions blocking the diffusion and vacancies trapping them in the goethite structure. The consequence of the diffusive behavior is that a part of He diffuses out of the crystal until sufficient damage accumulated along the b-axis. The diffusion domain size is the channel length along the b-axis rather than the whole crystallite size. To correct the He loss this study proposes estimation of the He retention and needed corrections for different types of goethite.