Cathodoluminescence, electron microscopy, and Raman spectroscopy of experimentally shock-metamorphosed zircon

Thorough understanding of the shock metamorphic signatures of zircon could be the basis for the use of this mineral as a powerful tool for the study of old, deeply eroded, and metamorphically overprinted impact structures and formations. This study of the cathodoluminescence (CL) and Raman spectroscopic signatures of experimentally (20-60 GPa) shock-metamorphosed zircon single crystals contributes to the understanding of high-pressure microdeformation in zircon. For all samples, an inverse relationship between the brightness of the backscattered electron (BSE) signal and the corresponding cathodoluminescence intensity was observed. The unshocked sample shows crosscutting, irregular fractures. The 20 GPa sample displays some kind of mosaic texture of CL brighter and darker domains, but does not exhibit any shock metamorphic features in BSE or CL images. The 40 GPa sample shows a high density of lamellar features, which might be explained by the phase transformation between zircon- and scheelite-structure phases of zircon and resulting differences in the energy levels of the activator elements. The CL spectra of unshocked and shocked (20, 40, and 60 GPa) zircon samples are dominated by narrow emission lines and broad bands in the region of visible light and in the near-UV range. The emission lines result from rare earth element activators and the broad bands might be associated with lattice defects. Raman spectra revealed that the unshocked and 20 GPa samples represent zircon-structure material, whereas the 40 GPa sample yielded additional peaks with relatively high peak intensities, which are indicative of the presence of the scheelite-type high-pressure phase. The 60 GPa sample has a Raman signature that is similar to that of an amorphous phase, in contrast to the observations of an earlier TEM study that the crystalline scheelite-structure phase is stable at this shock pressure. The 60 GPa Raman signature cannot be explained at this stage. The results show a clear dependence of the CL and Raman properties of zircon on shock pressure, which confirm the possible usage of these methods as shock indicators.