Transuranic Contamination in Sediment and Groundwater at the U.S. DOE Hanford Site

A review of transuranic radionuclide contamination in sediments and groundwater at the DOE’s Hanford Site was conducted. The review focused primarily on plutonium-239/240 and americium-241; however, other transuranic nuclides were discussed as well, including neptunium-237, plutonium-238, and plutonium-241. The scope of the review included liquid process wastes intentionally disposed to constructed waste disposal facilities such as trenches and cribs, burial grounds, and unplanned releases to the ground surface. The review did not include liquid wastes disposed to tanks or solid wastes disposed to burial grounds. It is estimated that over 11,800 Ci of plutonium-239, 28,700 Ci of americium-241, and 55 Ci of neptunium-237 have been disposed as liquid waste to the near surface environment at the Hanford Site. Despite the very large quantities of transuranic contaminants disposed to the vadose zone at Hanford, only minuscule amounts have entered the groundwater. Currently, no wells onsite exceed the DOE derived concentration guide for plutonium-239/240 (30 pCi/L) or any other transuranic contaminant in filtered samples. The DOE derived concentration guide was exceeded by a small fraction in unfiltered samples from one well (299-E28-23) in recent years (35.4 and 40.4 pCi/L in FY 2006). The primary reason that disposal of these large quantities of transuranic radionuclides directly to the vadose zone at the Hanford Site has not resulted in widespread groundwater contamination is that under the typical oxidizing and neutral to slightly alkaline pH conditions of the Hanford vadose zone, transuranic radionuclides (plutonium and americium in particular) have a very low solubility and high affinity for surface adsorption to mineral surfaces common within the Hanford vadose zone. Other important factors are the fact that the vadose zone is typically very thick (hundreds of feet) and the net infiltration rate is very low due to the desert climate. In some cases where transuranic radionuclides have been co-disposed with acidic liquid waste, transport through the vadose zone for considerable distances has occurred. For example, at the 216-Z-9 Crib, plutonium-239 and americium-241 have moved to depths in excess of 36 m (118 ft) bgs. Acidic conditions increase the solubility of these contaminants and reduce adsorption to mineral surfaces. Subsequent neutralization of the acidity by naturally occurring calcite in the vadose zone (particularly in the Cold Creek unit) appears to have effectively stopped further migration. The vast majority of transuranic contaminants disposed to the vadose zone on the Hanford Site (10,200 Ci [86%] of plutonium-239; 27,900 Ci [97%] of americium-241; and 41.8 Ci [78%] of neptunium-237) were disposed in sites within the PFP Closure Zone. This closure zone is located within the 200 West Area (see Figures 1.1 and 3.1). Other closure zones with notably high quantities of transuranic contaminant disposal include the T Farm Zone with 408 Ci (3.5%) plutonium-239, the PUREX Zone with 330 Ci (2.8%) plutonium-239, 200-W Ponds Zone with 324 Ci (2.8%) plutonium-239, B Farm Zone with 183 Ci (1.6%) plutonium-239, and the REDOX Zone with 164 Ci (1.4%) plutonium 239. Characterization studies for most of the sites reviewed in the document are generally limited. The most prevalent characterization methods used were geophysical logging methods. Characterization of a number of sites included laboratory analysis of borehole sediment samples specifically for radionuclides and other contaminants, and geologic and hydrologic properties. In some instances, more detailed research level studies were conducted. Results of these studies were summarized in the document

Geochemical Implications of CO2 Leakage Associated with Geologic Storage: A Review

Leakage from deep storage reservoirs is a major risk factor associated with geologic sequestration of carbon dioxide (CO2). Different scientific theories exist concerning the potential implications of such leakage for near-surface environments. The authors of this report reviewed the current literature on how CO2 leakage (from storage reservoirs) would likely impact the geochemistry of near surface environments such as potable water aquifers and the vadose zone. Experimental and modeling studies highlighted the potential for both beneficial (e.g., CO2 re sequestration or contaminant immobilization) and deleterious (e.g., contaminant mobilization) consequences of CO2 intrusion in these systems. Current knowledge gaps, including the role of CO2-induced changes in redox conditions, the influence of CO2 influx rate, gas composition, organic matter content and microorganisms are discussed in terms of their potential influence on pertinent geochemical processes and the potential for beneficial or deleterious outcomes. Geochemical modeling was used to systematically highlight why closing these knowledge gaps are pivotal. A framework for studying and assessing consequences associated with each factor is also presented in Section 5.6

Subsurface Behavior of Plutonium and Americium at Non-Hanford Sites and Relevance to Hanford

Seven sites where Pu release to the environment has raised significant environmental concerns have been reviewed. A summary of the most significant hydrologic and geochemical features, contaminant release events and transport processes relevant to Pu migration at the seven sites is presented

Contaminant Release Data Package for Residual Waste in Single-Shell Hanford Tanks

The Hanford Federal Facility Agreement and Consent Order requires that a Resource Conservation and Recovery Act (RCRA) Facility Investigation report be submitted to the Washington State Department of Ecology. The RCRA Facility Investigation report will provide a detailed description of the state of knowledge needed for tank farm performance assessments. This data package provides detailed technical information about contaminant release from closed single-shell tanks necessary to support the RCRA Facility Investigation report. It was prepared by Pacific Northwest National Laboratory (PNNL) for CH2M HILL Hanford Group, Inc., which is tasked by the U.S. Department of Energy (DOE) with tank closure. This data package is a compilation of contaminant release rate data for residual waste in the four Hanford single-shell tanks (SSTs) that have been tested (C-103, C-106, C-202, and C-203). The report describes the geochemical properties of the primary contaminants of interest from the perspective of long-term risk to groundwater (uranium, technetium-99, iodine-129, chromium, transuranics, and nitrate), the occurrence of these contaminants in the residual waste, release mechanisms from the solid waste to water infiltrating the tanks in the future, and the laboratory tests conducted to measure release rates

Applicability of the Linear Sorption Isotherm Model to Represent Contaminant Transport Processes in Site-Wide Performance Assessments

This paper addresses the applicability of the linear sorption model to the complex wastes of the Hanford Site

Status Report on Transfer of Physical and Hydraulic Properties Databases to the Hanford Environmental Information System - PNNL Remediation Decision Support Project, Task 1, Activity 6

This document provides a status report on efforts to transfer physical and hydraulic property data from PNNL to CHPRC for incorporation into HEIS. The Remediation Decision Support (RDS) Project is managed by Pacific Northwest National Laboratory (PNNL) to support Hanford Site waste management and remedial action decisions by the U.S. Department of Energy and their contractors. The objective of Task 1, Activity 6 of the RDS project is to compile all available physical and hydraulic property data for sediments from the Hanford Site, to port these data into the Hanford Environmental Information System (HEIS), and to make the data web-accessible to anyone on the Hanford Local Area Network via the so-called Virtual Library. These physical and hydraulic property data are used to estimate parameters for analytical and numerical flow and transport models that are used for site risk assessments and evaluation of remedial action alternatives. In past years efforts were made by RDS project staff to compile all available physical and hydraulic property data for Hanford sediments and to transfer these data into SoilVision{reg_sign}, a commercial geotechnical software package designed for storing, analyzing, and manipulating soils data. Although SoilVision{reg_sign} has proven to be useful, its access and use restrictions have been recognized as a limitation to the effective use of the physical and hydraulic property databases by the broader group of potential users involved in Hanford waste site issues. In order to make these data more widely available and useable, a decision was made to port them to HEIS and to make them web-accessible via a Virtual Library module. In FY08 the original objectives of this activity on the RDS project were to: (1) ensure traceability and defensibility of all physical and hydraulic property data currently residing in the SoilVision{reg_sign} database maintained by PNNL, (2) transfer the physical and hydraulic property data from the Microsoft Access database files used by SoilVision{reg_sign} into HEIS, which is currently being maintained by CH2M-Hill Plateau Remediation Company (CHRPC), (3) develop a Virtual Library module for accessing these data from HEIS, and (4) write a User's Manual for the Virtual Library module. The intent of these activities is to make the available physical and hydraulic property data more readily accessible and useable by technical staff and operable unit managers involved in waste site assessments and remedial action decisions for Hanford. In FY08 communications were established between PNNL and staff from Fluor-Hanford Co. (who formerly managed HEIS) to outline the design of a Virtual Library module that could be used to access the physical and hydraulic property data that are to be transferred into HEIS. Data dictionaries used by SoilVision{reg_sign} were also provided to Fluor-Hanford personnel who are now with CHPRC. During ongoing work to ensure traceability and defensibility of all physical and hydraulic property data that currently reside in the SoilVision{reg_sign} database, it was recognized that further work would be required in this effort before the data were actually ported into HEIS. Therefore work on the Virtual Library module development and an accompanying User's Guide was deferred until an unspecified later date. In FY09 efforts have continued to verify the traceability and defensibility of the physical and hydraulic property datasets that are currently being maintained by PNNL. Although this is a work in progress, several of these datasets are now ready for transfer to CHRPC for inclusion in HEIS. The actual loading of data into HEIS is performed by CHPRC staff, so after the data are transferred from PNNL to CHPRC, it will be the responsibility of CHPRC to ensure that these data are loaded and made accessible. This document provides a status report on efforts to transfer physical and hydraulic property data from PNNL to CHPRC for incorporation into HEIS

Combined Estimation of Hydrogeologic Conceptual Model and Parameter Uncertainty

The objective of the research described in this report is the development and application of a methodology for comprehensively assessing the hydrogeologic uncertainties involved in dose assessment, including uncertainties associated with conceptual models, parameters, and scenarios. This report describes and applies a statistical method to quantitatively estimate the combined uncertainty in model predictions arising from conceptual model and parameter uncertainties. The method relies on model averaging to combine the predictions of a set of alternative models. Implementation is driven by the available data. When there is minimal site-specific data the method can be carried out with prior parameter estimates based on generic data and subjective prior model probabilities. For sites with observations of system behavior (and optionally data characterizing model parameters), the method uses model calibration to update the prior parameter estimates and model probabilities based on the correspondence between model predictions and site observations. The set of model alternatives can contain both simplified and complex models, with the requirement that all models be based on the same set of data. The method was applied to the geostatistical modeling of air permeability at a fractured rock site. Seven alternative variogram models of log air permeability were considered to represent data from single-hole pneumatic injection tests in six boreholes at the site. Unbiased maximum likelihood estimates of variogram and drift parameters were obtained for each model. Standard information criteria provided an ambiguous ranking of the models, which would not justify selecting one of them and discarding all others as is commonly done in practice. Instead, some of the models were eliminated based on their negligibly small updated probabilities and the rest were used to project the measured log permeabilities by kriging onto a rock volume containing the six boreholes. These four projections, and associated kriging variances, were averaged using the posterior model probabilities as weights. Finally, cross-validation was conducted by eliminating from consideration all data from one borehole at a time, repeating the above process, and comparing the predictive capability of the model-averaged result with that of each individual model. Using two quantitative measures of comparison, the model-averaged result was superior to any individual geostatistical model of log permeability considered

Geochemical Characterization 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 (SST) 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 information available for the vadose zone beneath the SST farms and the Integrated Disposal Facility (IDF)

Decision Document for the Storm Water Outfalls/Industrial Wastewater Treatment Plant, Pesticide Rinse Area, Old Fire Fighting Training Pit, Illicit PCB Dump Site, and the Battery Acid Pit Fort Lewis, Washington

PNNL conducted independent site evaluations for four sites at Fort Lewis, Washington, to determine their suitability for closure on behalf of the installation. These sites were recommended for ''No Further Action'' by previous investigators and included the Storm Water Outfalls/Industrial Waste Water Treatment Plant (IWTP), the Pesticide Rinse Area, the Old Fire Fighting Training Pit, and the Illicit PCB Dump Site

FY12 ARRA-NRAP Report ? Studies to Support Risk Assessment of Geologic Carbon Sequestration

This report summarizes results of research conducted during FY2012 to support the assessment of environmental risks associated with geologic carbon dioxide (CO2) sequestration and storage. Several research focus areas are ongoing as part of this project. This includes the quantification of the leachability of metals and organic compounds from representative CO2 storage reservoir and caprock materials, the fate of metals and organic compounds after release, and the development of a method to measure pH in situ under supercritical CO2 (scCO2) conditions. Metal leachability experiments were completed on 6 different rock samples in brine in equilibrium with scCO2 at representative geologic reservoir conditions. In general, the leaching of RCRA metals and other metals of concern was found to be limited and not likely to be a significant issue (at least, for the rocks tested). Metals leaching experiments were also completed on 1 rock sample with scCO2 containing oxygen at concentrations of 0, 1, 5, and 10% to simulate injection of CO2 originating from the oxy-fuel combustion process. Significant differences in the leaching behavior of certain metals were observed when oxygen is present in the CO2. These differences resulted from oxidation of sulfides, release of sulfate, ferric iron and other metals, and subsequent precipitation of iron oxides and some sulfates such as barite. Experiments to evaluate the potential for mobilization of organic compounds from representative reservoir materials and cap rock and their fate in porous media (quartz sand) have been conducted. Results with Fruitland coal and Gothic shale indicate that lighter organic compounds were more susceptible to mobilization by scCO2 compared to heavier compounds. Alkanes demonstrated very low extractability by scCO2. No significant differences were observed between the extractability of organic compounds by dry or water saturated scCO2. Reaction equilibrium appears to have been reached by 96 hours. When the scCO2 was released from the reactor, less than 60% of the injected lighter compounds (benzene, toluene) were transported through dry sand column by the CO2, while more than 90% of the heavier organics were trapped in the sand column. For wet sand columns, most (80% to 100%) of the organic compounds injected into the sand column passed through, except for naphthalene which was substantial removed from the CO2 within the column. A spectrophotometric method was developed to measure pH in brines in contact with scCO2. This method provides an alternative to fragile glass pH electrodes and thermodynamic modeling approaches for estimating pH. The method was tested in simulated reservoir fluids (CO2–NaCl–H2O) at different temperatures, pressures, and ionic strength, and the results were compared with other experimental studies and geochemical models. Measured pH values were generally in agreement with the models, but inconsistencies were present between some of the models