Trace hydrogen zoning in diopside

Summary ¶The trace hydrogen content of a colourless to light-green zoned diopside single-crystal from Zillertal was investigated by IR microspectroscopy. The light-green part of the crystal reveals pleochroic OH absorption bands centred at 3645, 3463, and 3358cm^–1 which are attributed to structural OH defects. The OH absorptions of the colourless crystal part are characterised by weak bands at 3645 and 3662cm^–1 and by a strong band at 3676cm^–1. The bands at 3662 and 3676cm^–1 are attributed to the presence of amphibole lamellae. The analytical water content due to the structural OH defect concentration of the light-green crystal part amounts to 0.0016wt.%, that of the colourless part is lowered by a factor of about 50. According to optical absorption spectra, the light-green colour of the crystal is essentially caused by an Fe²⁺–Fe³⁺ charge transfer. The relatively high concentration of OH defects in the light-green crystal part associated with higher Al contents relative to the colourless part suggests that OH is incorporated as hydrodiopside component, CaMg(SiAlO₅OH). It is concluded that increasing water activity during the crystallisation process causes the formation of amphibole lamellae under consumption of nearly all of the water available in the fluid phase. It is further concluded that the observed hydrogen content of diopside represents a primary incorporation and not the result of late hydrothermal alteration processes.Received July 11, 2002; accepted October 30, 2002Published online February 24, 2003