Review of Techniques to Characterize the Distribution of Chromate Contamination in the Vadose Zone of the 100 Areas at the Hanford Site

The purpose of this report is to identify and evaluate the state-of-the-art techniques for characteriza¬tion of chromate contamination in the vadose zone of the 100 Areas at the Hanford Site. The techniques include direct techniques for analysis of chromium in the subsurface as well as indirect techniques to identify contamination through geophysical properties, soil moisture, or co-contaminants. Characteri¬zation for the distribution of chromium concentration in the vadose zone is needed to assess potential sources for chromate contamination plumes in groundwater at the 100-D, 100-K, and 100-B/C Areas

Isotopic Tracking of Hanford 300 Area Derived Uranium in the Columbia River

Our objectives in this study are to quantify the discharge rate of uranium (U) to the Columbia River from the Hanford Site's 300 Area, and to follow that U down river to constrain its fate. Uranium from the Hanford Site has variable isotopic composition due to nuclear industrial processes carried out at the site. This characteristic makes it possible to use high-precision isotopic measurements of U in environmental samples to identify even trace levels of contaminant U, determine its sources, and estimate discharge rates. Our data on river water samples indicate that as much as 3.2 kg/day can enter the Columbia River from the 300 Area, which is only a small fraction of the total load of dissolved natural background U carried by the Columbia River. This very low-level of Hanford derived U can be discerned, despite dilution to < 1 percent of natural background U, 350 km downstream from the Hanford Site. These results indicate that isotopic methods can allow the amounts of U from the 300 Area of the Hanford Site entering the Columbia River to be measured accurately to ascertain whether they are an environmental concern, or are insignificant relative to natural uranium background in the Columbia River

Screening of Potential Remediation Methods for the 200-BP-5 Operable Unit at the Hanford Site

A screening-level evaluation of potential remediation methods for application to the contaminants of concern (COC) in the 200-BP-5 Operable Unit at the Hanford Site was conducted based on the methods outlined in the Guidance for Conducting Remedial Investigations and Feasibility Studies under CERCLA Interim Final (EPA 1988). The scope of this screening was to identify the most promising remediation methods for use in the more detailed analysis of remediation alternatives that will be conducted as part of the full feasibility study. The screening evaluation was conducted for the primary COC (potential major risk drivers) identified in the groundwater sampling and analysis plan for the operable unit (DOE/RL-2001-49, Rev. 1) with additions

Isotopic Tracers for Biogeochemical Processes and Contaminant Transport: Hanford, Washington

Our goal is to use isotopic measurements to understand how contaminants are introduced to and stored in the vadose zone, and what processes control migration from the vadose zone to groundwater and then to surface water. We have been using the Hanford Site in south-central Washington as our field laboratory, and our investigations are often stimulated by observations made as part of the groundwater monitoring program and vadose zone characterization activities. Understanding the transport of contaminants at Hanford is difficult due to the presence of multiple potential sources within small areas, the long history of activities, the range of disposal methods, and the continuing evolution of the hydrological system. Observations often do not conform to simple models, and cannot be adequately understood with standard characterization approaches, even though the characterization activities are quite extensive. One of our objectives is to test the value of adding isotopic techniques to the characterization program, which has the immediate potential benefit of addressing specific remediation issues, but more importantly, it allows us to study fundamental processes at the scale and in the medium where they need to be understood. Here we focus on two recent studies at the waste management area (WMA) T-TX-TY, which relate to the sources and transport histories of vadose zone and groundwater contamination and contaminant fluid-sediment interaction. The WMA-T and WMA-TX-TY tank farms are located within the 200 West Area in the central portion of the Hanford Site (Fig. 2). They present a complicated picture of mixed groundwater plumes of nitrate, {sup 99}Tc, Cr{sup 6+}, carbon tetrachloride, etc. and multiple potential vadose zone sources such as tank leaks and disposal cribs (Fig. 3). To access potential vadose zone sources, we analyzed samples from cores C3832 near tank TX-104 and from C4104 near tank T-106. Tank T-106 was involved in a major event in 1973 in which 435,000 L of high activity waste leaked to the vadose zone over a seven-week period. Other nearby tanks (T-103 and T-101) are also suspected of having leaked or overfilled. Pore water from these cores was analyzed for U and Sr isotopic compositions. Increasing {sup 99}Tc concentration in monitoring well 299-W11-39 (to 27,000 pCi/L in 2005) near the northeast corner of the WMA-T area prompted the emplacement of a series of new wells, 299-W11-25B, W11-45 (down gradient), and W11-47 (Fig. 3), during which depth discrete samples were collected below the groundwater surface. The depth profile from W11-25B revealed high {sup 99}Tc concentrations peaking at 182,000 pCi/L at {approx}10 m below the water table (Dresel et al. 2006). We obtained aliquots for isotopic analysis of groundwater samples produced by purge-and-pump sampling during the drilling of W11-25B, -45 and -47. In addition we have analyzed groundwater samples from monitoring wells in the vicinity of WMA T-TX-TY

Geochemical Processes Data Package for the Vadose Zone in the Single-Shell Tank Waste Management Areas at the Hanford Site

This data package discusses the geochemistry of vadose zone sediments beneath the single-shell tank farms at the U.S. Department of Energy’s (DOE’s) Hanford Site. The purpose of the report is to provide a review of the most recent and relevant geochemical process information available for the vadose zone beneath the single-shell tank farms and the Integrated Disposal Facility. Two companion reports to this one were recently published which discuss the geology of the farms (Reidel and Chamness 2007) and groundwater flow and contamination beneath the farms (Horton 2007)

Effect of Eucalyptus plantations, geology, and precipitation variability on water resources in upland intermittent catchments

Land-use change and climate variability have the potential to alter river flow and groundwater resources dramatically, especially by modifying actual evapotranspiration. Seven catchments with intermittent flow dominated by either winter-active perennial pastures (4 catchments) or Eucalyptus globulus plantations (3 catchments), located in 3 geologic settings of southeastern Australia, were studied for over 6 years to determine the primary controls on water resources. Groundwater levels in the pasture sites were stable through the 2011–2016 study period, while levels in the plantations declined in the same period. Streamflow occurred mainly during winter. Annual streamflow showed no difference clearly attributable to pasture versus plantation land use. The presence of grass buffers along streams enhances groundwater recharge and saturation-dependent overland flow, reducing the impacts of the plantations on streamflow. Site water balances indicated that the average annual actual evapotranspiration was 87–93% of precipitation for pasture catchments and 102–108% of precipitation for plantation catchments. Actual evapotranspiration greater than precipitation at the plantations was attributed to uptake of groundwater by the root system in parts of the catchments. Thus, change to groundwater storage is a critical component in the water balance. Actual evapotranspiration from pasture catchments was higher than previously estimated from global pasture and cropping data, instead matching global precipitation versus actual evapotranspiration curves for treed catchments

Geochemical Characterization of Chromate Contamination in the 100 Area Vadose Zone at the Hanford Site

The major objectives of the proposed study were to: 1.) determine the leaching characteristics of hexavalent chromium [Cr(VI)] from contaminated sediments collected from 100 Area spill sites; 2.) elucidate possible Cr(VI) mineral and/or chemical associations that may be responsible for Cr(VI) retention in the Hanford Site 100 Areas through the use of i.) macroscopic leaching studies and ii.) microscale characterization of contaminated sediments; and 3.) provide information to construct a conceptual model of Cr(VI) geochemistry in the Hanford 100 Area vadose zone. In addressing these objectives, additional benefits accrued were: (1) a fuller understanding of Cr(VI) entrained in the vadose zone that will that can be utilized in modeling potential Cr(VI) source terms, and (2) accelerating the Columbia River 100 Area corridor cleanup by providing valuable information to develop remedial action based on a fundamental understanding of Cr(VI) vadose zone geochemistry. A series of macroscopic column experiments were conducted with contaminated and uncontaminated sediments to study Cr(VI) desorption patterns in aged and freshly contaminated sediments, evaluate the transport characteristics of dichromate liquid retrieved from old pipelines of the 100 Area; and estimate the effect of strongly reducing liquid on the reduction and transport of Cr(VI). Column experiments used the < 2 mm fraction of the sediment samples and simulated Hanford groundwater solution. Periodic stop-flow events were applied to evaluate the change in elemental concentration during time periods of no flow and greater fluid residence time. The results were fit using a two-site, one dimensional reactive transport model. Sediments were characterized for the spatial and mineralogical associations of the contamination using an array of microscale techniques such as XRD, SEM, EDS, XPS, XMP, and XANES. The following are important conclusions and implications. Results from column experiments indicated that most of contaminant Cr travels fast through the sediments and appears as Cr(VI) in the effluents. The significance of this for groundwater concentrations would, however, depend on the mass flux of recharge to the water table. adsorption of Cr(VI) to sediments from spiked Cr(VI) solution is low; calculated retardation coefficients are close to one. Calcium polysulfide solutions readily reduced Cr(VI) to Cr(III) in column experiments. However a significant amount of the Cr(VI) was mobilized ahead of the polysulfide solution front. This has significant implications for in-situ reductive remediation techniques. The experiments suggest that it would be difficult to design a remedial measure using infiltration of liquid phase reductants without increasing transport of Cr(VI) toward the water table. The microscopic characterization results are consistent with the column studies. Cr(VI) is found as ubiquitous coatings on sediment grain surfaces. Small, higher concentration, chromium sites are associated with secondary clay mineral inclusions, with occasional barium chromate minerals, and reduced to Cr(III) in association with iron oxides that are most likely magnetite primary minerals. Within the restricted access domains of sediment matrix, ferrous iron could also diffuse from in situ, high-surface-area minerals to cause the reductive immobilization of chromate. This process may be favored at microscale geochemical zones where ferrous iron could be supplied. Once nucleated, micrometer-scale precipitates are favored as growing locales for further accumulation, causing the formation of discrete zones of Cr(III)

Environmental application of stable xenon and radioxenonmonitoring

Characterization of transuranic waste is needed to makedecisions about waste site remediation. Soil-gas sampling for xenonisotopes can be used to define the locations of spent fuel andtransuranic wastes. Radioxenon in the subsurface is characteristic oftransuranic waste and can be measured with extreme sensitivity usinglarge-volume soilgas samples. Measurements at the Hanford Site showed133Xe and 135Xe levels indicative of 240Pu spontaneous fission. Stablexenon isotopic ratios from fission are distinct from atmospheric xenonbackground. Neutron capture by 135Xe produces an excess of 136Xe inreactor-produced xenon providing a means of distinguishing spent fuelfrom separated transuranic materials

Linking evapotranspiration seasonal cycles to the water balance of headwater catchments with contrasting land uses

Land use affects evapotranspiration rates and is a primary driver of the catchment water balance. The water balance of two catchments in southeastern Australia dominated by either grazed pasture or blue gum (Eucalyptus globulus) plantation was studied, focusing on the patterns of evapotranspiration (ET) throughout the year. Rainfall, streamflow, and groundwater levels measured between 2015 and 2019 were combined to estimate annual ET using a water balance equation. In the pasture, eddy covariance was used to measure ET from the catchment. Sap flow measurements were used to estimate tree transpiration in May 2017–May 2018 and Feb 2019–Feb 2021 in two different plots within the plantation. The tree transpiration rates were added to interception, estimated as a percentage of annual rainfall, to calculate ET from the plantation catchment. ET in the pasture showed strong seasonal cycles with very low ET rates in summer and ET rates in spring that were larger than the transpiration rates in the plantation, where trees transpired consistently throughout the year. The estimated annual ET from the water balance equation was comparable to ET estimated from other measurements. In the pasture, ET on average accounted for 88% of annual rainfall, while ET in the plantation was on average 93% of rainfall, exceeding it in the years with annual rainfall lower than about 500 mm. The difference between the ET rates in the plantation and the pasture was approximately 30–50 mm y−1. The larger ET rates in the plantation were reflected in a gradual decrease in the groundwater storage. The larger ET rates were enough to cause a decrease in groundwater storage in the plantation but not in the pasture, where groundwater levels remained stable