A series of natural rhyolitic obsidians were analyzed for their total water contents by a vacuum extraction technique. The grain size of the crushed samples can significantly affect these analyses. Coarse powders must be used in order to avoid surface-correlated water. These analyses were used to calibrate infrared spectroscopic measurements of water in glass using several infrared and near-infrared absorption bands. We demonstrate that infrared spectroscopy can yield precise determinations of not only total dissolved water contents, but also the concentrations of individual H-bearing species in natural and synthetic rhyolitic glasses on spots as small as a few tens of micrometers in diameter.