Supergene phases from ferruginous duricrusts: non-destructive microsampling and mineralogy prior to (U–Th) ∕ He geochronological analysis

Abstract

Interpreting the ages of supergene mineralogical phases in laterite is complex because they consist of polycrystalline mixtures of different phases at the microscopic scale that could be crystalized at different epochs. Among the geochronometers, the (U-Th)/He method on hematite and goethite is more often used, but ages can be difficult to interpret due to phases mixing. To resolve this issue, this study proposes a methodology for performing detailed mineralogical analysis of hematite and goethite single grains prior to their dating using the (U-Th)/He method. Strictly non-destructive mineralogy of single grains is not achievable by classical tools, such as conventional powder XRD (X-ray diffraction; requiring at least some milligrams of powder) or SEM (scanning electron microscopy; that can contaminate the grain by coating or fixing). Therefore, we performed X-ray diffraction patterns of single grains using high-flux X-ray beams from both a rotating anode (XRD_rotat) laboratory diffractometer and a synchrotron beamline (XRD_synch) and compared the results in order to design a method based on XRD_rotat only. For this purpose, two samples from the pisolitic facies of a Brazilian ferruginous duricrust (Alto Paranaíba region, Minas Gerais State, Brazil) were chosen because they presented a usual heterogeneity. Rietveld refinements of the XRD patterns obtained from both XRD_rotat and XRD_synch yielded similar results for the weight percentage ratio of the main phases and mean coherent domain sizes and less similar results for Al substitution rates, thus validating the XRD_rotat approach. No beam damage was observed when increasing X-ray exposure time, neither on XRD patterns nor on (U-Th)/He ages. Hence, sub-millimeter, undisturbed grains can be used to analyze the mineralogy of ferruginous duricrusts by XRD_rotat with a short exposure, and the same grains can subsequently be dated by (U-Th)/He geochronology analysis. The (U-Th)/He dating of pisolitic core and cortex grains also provided meaningful ages: they revealed two evolution phases of the ferruginous duricrust, which occurred at or before the Oligocene for the pisolitic core and middle Miocene for the pisolitic cortex, agreeing with the previous model for the development of pisolites. The mineralogy of single grains selected for dating is helpful for discussing the crystallization ages, and the high-flux XRD approach may be applied to other supergene mineral parageneses used for absolute dating.