Mineral evolution is concerned with the timing of mineral occurrences, such as the earliest reported occurrences in the geologic record. Minerals containing essential Li have not been reported from rocks older than ca. 3000 Ma, thus the lithian tourmaline (fluor-elbaite) and mica (lepidolite) assemblage from a pegmatite near Zishineni associated with the ca. 3000 Ma Sinceni Pluton presents unusual interest. Fluor-elbaite (0.75-0.98 F per formula unit) forms green crystals up to 50 mm long. Spindle stage measurements give v = 1.652(1), e = 1.627(1) (589.3 nm). Optical absorption spectroscopy shows Fe and Mn are divalent; infra-red spectroscopy demonstrates the presence of Li and indicates the presence of (OH) at both the (OH) sites. Electron microprobe analysis of 330 points on several prisms, the largest of which is zoned in Fe and Ca, gives the following average and standard deviations in wt%: SiO 2 37.29 (0.26), TiO 2 0.05 (0.05), Al 2 O 3 38.14 (0.35), Cr 2 O 3 0 (0.02), MgO 0.02 (0.01), MnO 3.57 (0.25), FeO 2.48 (0.60), Na 2 O 2.48 (0.09), K 2 O 0.03 (0.12), CaO 0.77 (0.21), F 1.80 (0.11), Cl 0 (0.01) wt%. Nuclear reaction analyses gave Li 2 O 0.91 (0.04) and B 2 O 3 10.55 (0.45). The empirical formula of fluor-elbaite was determined by integrating crystal-chemical data from electron microprobe analysis, nuclear reaction analysis, crystal structure refinement using X-ray diffraction, infra-red and optical absorption spectroscopy:
Traditional methods to measure water in nominally anhydrous minerals (NAMs) are, for example, Fourier transformed infrared (FTIR) spectroscopy or secondary ion mass spectrometry (SIMS). Both well-established methods provide a low detection limit as well as high spatial resolution yet may require elaborate sample orientation or destructive sample preparation. Here we analyze the water content in erupted volcanic clinopyroxene phenocrysts by proton-proton scattering and reproduce water contents measured by FTIR spectroscopy. We show that this technique provides significant advantages over other methods as it can provide a three-dimensional distribution of hydrogen within a crystal, making the identification of potential inclusions possible as well as elimination of surface contamination. The sample analysis is also independent of crystal structure and orientation and independent of matrix effects other than sample density. The results are used to validate the accuracy of wavenumber-dependent vs. mineral-specific molar absorption coefficients in FTIR spectroscopy. In addition, we present a new method for the sample preparation of very thin crystals suitable for proton-proton scattering analysis using relatively low accelerator potentials.
Ion beam analysis has for decades been used as a tool for geochemical analysis of trace elements using both X-rays (particle induced X-ray emission) and nuclear reaction analysis. With the geoanalytical setup at the Lund Ion Beam Analysis Facility, the boron content in geological samples with a spatial resolution of 1 µm is determined through nuclear reaction analysis. In the newly upgraded setup, a single detector has been replaced by a double sided silicon strip detector with 2048 segments. After optimization, boron content in geological samples as low as 1 µg g−1 can be measured.
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