Highly Sensitive Nondestructive Rare Earth Element Detection by Means of Wavelength-Dispersive X-ray Fluorescence Spectroscopy Enabled by an Energy Dispersive pn-Charge-Coupled-Device Detector

Detection of rare earth elements (REE) is commonly performed with destructive techniques such as (LA)-ICPMS or coupled to a destructive sample preparation. When investigating unique geological samples, such as cometary, asteroidal, or interstellar material from sample return missions or inclusions in deep Earth diamonds, a nondestructive method is preferred. The presented nondestructive highly sensitive wavelength-dispersive X-ray fluorescence spectroscopy (WD-XRF) technique is designed to measure the L-lines of REE between 4.5 and 7 keV with a sensitivity down to the ppm level. REE fluorescence L-lines are often only separated by a few eV from neighboring XRF-lines and cannot be resolved by an energy dispersive approach especially in the presence of transition metal K-lines. In our spectrometer the characteristic X-rays emitted by the sample are dispersed by a fixed Ge(111) analyzer crystal over the active area of an energy dispersive pn-charge-coupled-device (pnCCD) detector, enabling high energy resolution detection of X-rays differentiated by their corresponding Bragg angles. The use of an energy-dispersive 2D detector enables the simultaneous acquiring of XRF-lines while eliminating any ambiguities due to potential contribution from higher order diffraction effects or other diffraction planes and thereby increases the sensitivity by reducing the (scatter) background. This detection method shows an energy resolution of 12 eV for the Ti-K alpha fluorescence line and has a sensitivity down to 0.50 ppm for REE L-lines. The method was optimized specifically for the nondestructive analysis of inclusions in deep Earth diamonds, yielding in situ quantitative information about up-to-now inaccessible elemental (REE) composition patterns together with the more abundant transition metals like Ti, Cr, Mn, and Fe. This information is of great importance to decipher the role that deep Earth plays in the global carbon and fluid cycle.