This hydrology and geochemistry volume is a companion volume to the 2007 Geological Society of America Memoir 199, The Geology and Climatology of Yucca Mountain and Vicinity, Southern Nevada and California, edited by Stuckless and Levich. The work in both volumes was originally reported in the U.S. Department of Energy regulatory document Yucca Mountain Site Description, for the site characterization study of Yucca Mountain, Nevada, as the proposed U.S. geologic repository for high-level radioactive waste. The selection of Yucca Mountain resulted from a nationwide search and numerous committee studies during a period of more than 40 yr. The waste, largely from commercial nuclear power reactors and the government's nuclear weapons programs, is characterized by intense penetrating radiation and high heat production, and, therefore, it must be isolated from the biosphere for tens of thousands of years. The extensive, unique, and often innovative geoscience investigations conducted at Yucca Mountain for more than 20 yr make it one of the most thoroughly studied geologic features on Earth. The results of these investigations contribute extensive knowledge to the hydrologic and geochemical aspects of radioactive waste disposal in the unsaturated zone. The science, analyses, and interpretations are important not only to Yucca Mountain, but also to the assessment of other sites or alternative processes that may be considered for waste disposal in the future. Groundwater conditions, processes, and geochemistry, especially in combination with the heat from radionuclide decay, are integral to the ability of a repository to isolate waste. Hydrology and geochemistry are discussed here in chapters on unsaturated zone hydrology, saturated zone hydrology, paleohydrology, hydrochemistry, radionuclide transport, and thermally driven coupled processes affecting long-term waste isolation. This introductory chapter reviews some of the reasons for choosing to study Yucca Mountain as a repository site.