We investigate the retrieval of terrestrial precipitable water columns using a new spectral fitting method applied to Global Ozone Monitoring Experiment (GOME) data. The method is an optical absorption spectroscopy technique and employs a new approach to the opacity sampling of absorption line spectra which we apply to a little-studied visible band between 585 and 600 nm. The GOME-retrieved columns are compared with data from the European Center for Medium-Range Weather Forecasts for different orbits and show good agreement. The new retrieval algorithm is sensitive to the temperature and pressure dependence of absorption lines in general and may be easily applied to spectra of trace gases other than water vapor. ¿ 2000 American Geophysical Union