Spectroscopy of synthetic Mg-Fe pyroxenes I: Spin-allowed and spin-forbidden crystal field bands in the visible and near-infrared

Abstract

Understanding the fundamental crystal chemical controls on visible and near-infrared reflectance spectra of pyroxenes is critical to quantitatively assessing the mineral chemistry of pyroxenes viewed by remote sensing. This study focuses on the analysis ofspectroscopic measurements of a comprehensive set of synthetic Mg-Fe pyroxenes from the visible through the near-infrared (0.3-2.6 micrometers) to address the constraints of crystal structure and Fe^2+ content on spin-forbidden and spin-allowed crystal field absorptions in Ca-freeorthopyroxenes. The chemistry and oxidation state of the synthetic pyroxenes are characterized. Coordinated Mössbauer spectroscopy is used to determine site occupancy of Fe^2+ in the M1 and M2 crystallographic sites. Properties of visible and near-infrared absorption bands of the synthetic pyroxenes are quantified using the modified Gaussian model. The 1 and 2 m spin-allowed crystal field absorption bands move regularly with increasing iron content, defining a much tighter trend than observed previously. A spin-allowed crystal field absorption band at 1.2 micrometers is explicitly verified, even at low total iron contents, indicating that some portion of Fe^2+ resides in the M1 site. The 1.2 micrometers band intensifies and shifts to longer wavelengths with increasing iron content. At visible wavelengths, spin-forbidden crystal field absorptions are observed in all iron-bearing samples. The most prominent absorption near 506 nm, attributed to iron in the M2 site, shifts to slightly longer wavelengths with iron content. The purity and extent of this pyroxene series allows visible wavelength absorption bands to be directly assigned to specific transitions of Fe^2+ in the M1 and M2 sites.