Physicochemical relationships in the boundary zone between groundwater and surface water (i.e. the hyporheic zone) are controlled by surface water hydrology and the hydrogeologic properties of the riverbed. We studied how sediment permeability and river discharge altered the vertical hydraulic gradient (VHG) and water quality of the hyporheic zone within the Hanford Reach of the Columbia River. The Columbia River at Hanford is a large, cobble-bed river where water level fluctuates up to 2 m daily because of hydropower generation. Concomitant with river stage recordings, continuous readings were made of water temperature, specific conductance, dissolved oxygen and water level of the hyporheic zone. The water level data were used to calculate VHG between the river and hyporheic zone. Sediment permeability was estimated using slug tests conducted in piezometers installed into the river bed. The response of water quality measurements and VHG to surface water fluctuations varied widely among study sites, ranging from no apparent response to covariance with river discharge. At some sites, a hysteretic relationship between river discharge and VHG was indicated by a time lag in the response of VHG to changes in river stage. The magnitude, rate of change and hysteresis of the VHG response varied the most at the least permeable location (hydraulic conductivity (K) ¼ 2.9 Â 10 À4 cms À1 ) and the least at the most permeable location (K ¼ 8.8 Â 10 À3 cms À1 ). Our study provides empirical evidence that sediment properties and river discharge both control the water quality of the hyporheic zone. Regulated rivers, like the Columbia River at Hanford, that undergo large, frequent discharge fluctuations represent an ideal environment in which to study hydrogeologic processes over relatively short time periods (i.e. days to weeks) that would require much longer periods (i.e. months to years) to evaluate in unregulated systems.

Executive SummaryUranium (U) is an important risk-driving contaminant at the Hanford Site. Over 200,000 kg have been released to the vadose zone over the course of site operations, and a number of vadose zone and groundwater plumes containing the uranyl cation [UO 2 2+ , U(VI)] have been identified. U is recognized to be of moderate-to-high mobility, conditions dependent. The site is currently making decisions on several of these plumes with long-lasting implications, and others are soon to come.Uranium is one of nature's most intriguing and chemically complex elements. The fate and transport of U(VI) has been studied over the long lifetime of the Hanford Site by various contractors, along with the Pacific Northwest National Laboratory (PNNL) and its collaborators. Significant research has more recently been contributed by the national scientific community with support from the U.S. Department of Energy's (DOE) Office of Science through its Environmental Remediation Sciences Division (ERSD). This report represents a first attempt to integrate these findings into a cohesive view of the subsurface geochemistry of U at the Hanford Site. The objective is to inform all interested Hanford parties about the in-ground inventory of U and its geochemical behavior. This report also comments on the prospects for the development of a robust generic model to more accurately forecast future U(VI) migration at different Hanford waste sites, along with further research necessary to reach this goal.To accomplish the report objectives, the environmental geochemistry of U at the Hanford Site is discussed in terms of both the vadose and saturated zone, to the extent that it is known. Hexavalent uranium [U(VI)] is the dominant valence form of U under the predominantly oxidizing subsurface conditions at the Hanford Site, and the researchers' analyses consequently emphasize this species. The nature and concentration of background U in Hanford subsurface sediments is identified to place contaminant U(VI) concentrations and behavior in perspective to the natural system. In-ground U-waste inventories are quantified and characterized with regard to source term, to the extent possible, and the most important sites from an inventory perspective are identified. The U-isotopic content of various waste streams are discussed from the perspective of waste-source tracking. The geochemical attenuation processes responsible for slowing the rate of subsurface U migration, relative to the transporting water front, are illustrated through careful consideration of both field characterization studies of existing U vadose-zone and groundwater plumes, and laboratory studies of derived contaminated and uncontaminated sediments. Both empirical and more mechanistic models of these attenuation processes are considered as well as the parameters that define attenuation magnitude. Attention is given to the behavior of contaminant U(VI) that has been in contact with Hanford sediments for extended periods (circa 10-50 years), as long contact imparts unique characte...

2In the mid-1990s, a groundwater plume of uranium (U) was detected in monitoring wells in the B-BX-BY Waste Management Area (WMA) at the Hanford Site in Washington. This area has been used since the late 1940s to store high-level radioactive waste and other products of U fuel-rod processing. Using multiple collector ICP source magnetic sector mass spectrometry (MC ICPMS) high precision uranium isotopic analyses were conducted of samples of vadose zone contamination and of groundwater. The ratios 236 U/ 238 U, 234 U/ 238 U and 238 U/ 235 U are used to distinguish contaminant sources. Based on the isotopic data, the source of the groundwater contamination appears to be related to a 1951 overflow event at tank BX-102 that spilled high level U waste into the vadose zone. The U isotopic variation of the groundwater plume is a result of mixing between contaminant U from this spill and natural background U. Vadose zone U contamination at tank B-110 likely predates the recorded tank leak and can be ruled out as a source of groundwater contamination, based on the U isotopic composition. The locus of vadose zone contamination is displaced from the initial locus of groundwater contamination, indicating that lateral migration in the vadose zone was at least 8 times greater than vertical migration. The time evolution of the groundwater plume suggests an average U migration rate of ~0.7-0.8 m/day showing slight retardation relative to a ground water flow of ~1 m/day. IntroductionGroundwater contamination at the Hanford Site, in south-central Washington, resulted from decades of nuclear fuel production and processing. Understanding the fate and transport of contamination is hindered by the presence of multiple potential contamination sources within relatively small areas, and the extended 50-year duration of activity. Natural sources of uranium have a uniform 238 U/ 235 U ratio (with the rare exception of the Oklo natural fission reactor (1)), but can have variable 234 U/ 238 U depending on natural processes that can disturb the secular equilibrium of the 238 U decay chain. In contrast, anthropogenic U can have altered 238 U/ 235 U due either to 235 U enrichment for nuclear applications or to changes resulting from the burn up of natural or enriched uranium in nuclear reactors. In addition, the consumption of uranium fuel rods in reactors produces 236 U (half-life = 23 million years) through neutron capture by 235 U. 236 U does not occur naturally to any significant degree. These contrasts in the isotopic compositions of natural and anthropogenic uranium, as well as the wide variation in the isotopic composition 3 of different anthropogenic uranium sources, promotes the measurement of uranium isotopic composition as a tracer of uranium contamination in the environment (e.g., refs 2-4).Multiple collector ICP magnetic sector mass spectrometry (MC-ICPMS) provides high precision isotopic analyses of a wide range of elements (5, 6, also see overview 7). MC-ICPMS has been used for high precision 234 U/ 238 U measurements (8) and for...