and other DOE sites, field vadose zone observations have shown complex water seepage and mass transport behavior in a highly heterogeneous, thick vadose zone on a variety of scales. Recent investigation showed that severe contamination of soils and groundwater by organic contaminant and nuclear waste occurred because of water seepage and contaminant transport along localized, preferential, fast flow within the heterogeneous vadose zone. However, most of the existing characterization and monitoring methods are not able to locate these localized and persistent preferential pathways associated with specific heterogeneous geologic features, such as clastic dikes, caliche layers, or fractures. In addition, changes in the chemical composition of moving and indigenous solutes, particularly sodium concentration, redox conditions, biological transformation of organic materials, and high temperature, may significantly alter water, chemicals, and bio-transformation exchange between the zones of fast flow and the rest of the media. In this paper, using the data from Hanford and INEEL sites, we will (1) present evidence that central problems of the vadose zone investigations are associated with preferential, fast flow phenomena and accelerated migration of organic and radioactive elements, (2) identify gaps in current characterization and monitoring technologies, and (3) recommend actions for the development of advanced vadose zone characterization and monitoring methods using a combination of hydrologic, geochemical, and geophysical techniques.