Near-infrared spectra of clinopyroxenes: Effects of calcium content and crystal structure

Pyroxenes are among the most common minerals in the solar system and are ideally suited for remote geochemical analysis because of the sensitivity of their distinctive spectra to mineral composition. Fe is responsible for the dominant pyroxene absorptions in the visible and near-infrared, but substitutions of other cations such as Ca change the crystal structure and site geometries and thus the crystal field splitting energies of the Fe cations. To define spectral systematics resulting from major pyroxene cations (Ca, Mg, and Fe), we focus on a suite of pyroxenes synthesized with only Ca, Mg, and Fe in the two octahedral sites, specifically examining the effect of Ca on pyroxene absorption bands. The modified Gaussian model is used to deconvolve pyroxene spectra into component bands that can then be linked directly to crystal field absorptions. In orthopyroxenes and low-Ca clinopyroxenes, Ca-content has a strong and predictable effect on the positions of the absorption bands. At a threshold of Wo30, the crystal field environment stagnates and the M2 bands cease to change significantly as more Ca is added. At Wo50, when most of the M2 sites are filled by Ca , band positions do not change drastically, although the presence and strengths of the 1 and 2 lm bands are affected by even trace amounts of Fe in the M2 site. It is thus apparent that next-nearest neighbors and the distortions they impose on the pyroxene lattice affect the electronic states around the Fe cations and control absorption band properties.