The pressurized unsaturated flow (PUF) test is a new experimental method for the evaluation of the long-term corrosion behavior of waste forms and other engineered barrier materials. Essentially, the technique provides a means to flow water through a porous bed of test material or materials at elevated temperature and under hydraulically unsaturated conditions. Bulk volumetric content, effluent pH and electrical conductivity are monitored in real time using a computer control and data acquisition system. In previous papers, we have reported on the changes in bulk water content, effluent chemistry, and glass corrosion rates that result from the formation of alteration products during these tests. These measurements are now supplemented through the use of the ultracentrifugation apparatus (UFA) for hydraulic property measurements and highresolution, x-ray microtomography (XMT) to provide 3-D spatial and temporal imaging of water distribution and pore structure alteration during these tests. Quantitative changes in the water retention characteristic were correlated with the onset of zeolite formation in the tests. Extensive alteration of the glass resulted in cementation of the glass grains near the bottom of the column, which was observed in situ using the XMT.