GSA Connects 2021 in Portland, Oregon

Paper No. 60-1
Presentation Time: 2:30 PM-6:30 PM


TOMASIC, Patrick1, HEIMANN RIOS, Adriana1, ALONSO-PEREZ, Raquel2, DYAR, M. Darby3 and LANZIROTTI, Antonio4, (1)Geological Sciences, East Carolina University, 101 Graham Building, Greenville, NC 27858, (2)Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA 02138, (3)Dept. of Astronomy, Mount Holyoke College, South Hadley, MA 01075, (4)Center for Advanced Radiation Sources, University of Chicago, 5640 S. Ellis Avenue, Chicago, IL 60637

Beryl (Be3Al2Si6O18), a hexagonal cyclosilicate, forms valuable gem-quality colored crystals and is a source of the “critical mineral” beryllium. The highly priced green variety, emerald, owes its color to Fe2+, Fe3+, Cr3+, and V3+ impurities in beryl’s structure, whereas trace Fe2+ causes blue beryl, aquamarine, and Fe3+ darkens the blue color. However, variations in valence state, overall redox state and coordination environment for Fe, Cr, V, and Mn, and their relationship to color are yet to be fully understood. Cutting-edge, synchrotron radiation X-ray absorption spectroscopy (XAS) allows non-destructive determination of valence state and coordination geometry of elemental impurities in gem-quality crystals. In this study, characterization of K-pre-edges for Fe, Cr, V, and Mn by micro-X-ray absorption near-edge structure (XANES) spectroscopy was performed on emerald and other beryl varieties to determine variations in pre-edge peak intensities and peak ratios and their relationship with color.

Preliminary results of normalized micro-XANES Fe spectra for multiple spot analyses in different color zones within individual emerald crystals from Chivor, Colombia, analyzed in the same orientation show pre-edge Fe2+ and Fe3+ peaks of higher intensity and generally higher Fe3+/Fe2+ peak ratios in darker green color zones than in lighter green and colorless zones. Two pre-edge Cr peaks have higher intensity in green than in lighter zones within zoned crystals. A pre-edge V3+ peak varies in intensity in colorless and green zones, but further studies are needed. In a zoned aquamarine from Vietnam, pre-edge Fe2+ and Fe3+ peaks have higher intensity in darker blue zones than in lighter blue and colorless zones. Several emerald crystals analyzed with their c axis oriented at various angles with respect to the X-ray beam show variations in relative intensity of the two pre-edge peaks for Fe and for Cr in XANES spectra with orientation. Further detailed characterization of XANES Fe, Cr, V, and Mn pre-edges in emerald, aquamarine, yellow, green, red, and colorless beryl considering orientations effects will be ultimately used to characterize oxidation state-color relationships.