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The invention features an optical medium for calibrating UV absorbance detectors, methods for making such an optical medium, and methods for calibrating UV absorbance detectors using such a medium. The optical calibration medium includes a gel-sol silica glass monolith with a rare-earth dopant therein. The rare-earth dopant exhibits at least one spectral feature in at least the far UV range. The constituents of the gel-sol silica glass monolith are selected so the rare-earth doped sol-gel glass monolith exhibits a transmittance in the far UV range so each distinct spectral feature of the rare-earth dopant in the far UV range is discernable. The transmittance in a particular embodiment is at least about 50% at about 250 nm. The rare earth materials selected for use as dopants are those exhibiting a wide range of spectral features, preferably over a range from about 190 nm to about 700 nm and more particularly exhibit at least one distinct spectral feature in the range from about 190 nm to about 300 nm. In a specific embodiment, the rare-earth dopant includes atoms of erbium, having spectral features in a range from about 190 nm to about 650 nm and a distinguishable far UV spectral feature at about 257 nm.