Caustic radioactive wastes that have leaked at Hanford Site (Richland, WA) induce mineral dissolution and subsequent secondary precipitation that influence the fate and transport of contaminants present in the waste solutions. The effects of secondary mineral precipitates, formed after contacting solids with simulated caustic wastes, on the flow path changes and radionuclide immobilization were investigated by reacting quartz, a mixture of quartz and biotite, and a Hanford sediment (Warden soil: coarse-silty, mixed, superactive, mesic Xeric Haplocambids) with simulated caustic tank waste solution. Continuous Si dissolution and concomitant secondary mineral precipitation were the principal reactions observed in both batch and flow-through tests. Nitrate-cancrinite was the dominant secondary precipitate on mineral surfaces after 3- to 10-d reaction times in batch experiments. X-ray microtomography images of a reacted quartz column revealed that secondary precipitates cemented quartz grains together and modified pore geometry in the center of the column. Along the circumference of the packed column, however, quartz dissolution continuously occurred, suggesting that wastes that leaked from buried tanks in the past likely did not migrate vertically as modeled in risk assessments but rather the pathways likely changed to be dominantly horizontal on precipitation of secondary precipitate phases in the Hanford vadose zone. Based on batch equilibrium sorption results on the reacted sediments, the dominant secondary precipitates (cancrinites) on the mineral surfaces enhanced the sorption capacity of typical Hanford sediment for radionuclides 129I(-I), 79Se(VI), 99Tc(VII), and 90Sr(II), all of which are of major concern at the Hanford Site.