To support the selection of a waste form for the liquid secondary wastes from the Hanford Waste Immobilization and Treatment Plant, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing on four candidate waste forms. Two of the candidate waste forms have not been developed to scale as the more mature waste forms. This work describes engineering-scale demonstrations conducted on Ceramicrete and DuraLith candidate waste forms.Both candidate waste forms were successfully demonstrated at an engineering scale. A preliminary conceptual design could be prepared for full-scale production of the candidate waste forms. However, both waste forms are still too immature to support a detailed design. Formulations for each candidate waste form need to be developed so that the material has a longer working time after mixing the liquid and solid constituents together. Formulations optimized based on previous lab studies did not have sufficient working time to support large-scale testing. The engineering-scale testing was successfully completed using modified formulations. Further lab development and parametric studies are needed to optimize formulations with adequate working time and assess the effects of changes in raw materials and process parameters on the final product performance. Studies on effects of mixing intensity on the initial set time of the waste forms are also needed. v SummaryThe Hanford Site in southeast Washington State has 56 million gallons of radioactive and chemically hazardous wastes stored in 177 underground tanks (DOE 2010). The U.S. Department of Energy (DOE), Office of River Protection, through its contractors, is constructing the Hanford Tank Waste Treatment and Immobilization Plant (WTP) to convert the radioactive and hazardous wastes into stable glass waste forms for disposal. Within the WTP, the pretreatment facility will receive the retrieved waste from the tank farms and separate it into two treated process streams. These waste streams will be vitrified, and the resulting waste canisters will be sent to offsite (high-level waste [HLW]) and onsite (immobilized lowactivity waste [ILAW]) repositories. As part of the pretreatment and ILAW processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility (ETF) on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed in the Integrated Disposal Facility (IDF).To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions (WRPS) has initiated secondary-waste-form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is conducting tests on four candidate waste forms for stabilizing and solidifying WTP liquid secondary wastes:• Cast Stone Portland-cement-based waste form• Ceramicrete phosphate-b...

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Deep vadose zone environments can be a primary source and pathway for contaminant migration to groundwater. These environments present unique characterization and remediation challenges that necessitate scrutiny and research. The thickness, depth, and intricacies of the deep vadose zone, combined with a lack of understanding of the key subsurface processes (e.g., biogeochemical and hydrologic) affecting contaminant migration, make it difficult to create validated conceptual and predictive models of subsurface flow dynamics and contaminant behavior across multiple scales. These factors also make it difficult to design and deploy sustainable remedial approaches and monitor long-term contaminant behavior after remedial actions. Functionally, methods for addressing contamination must remove and/or reduce transport of contaminants. This problem is particularly challenging in the arid western United States where the vadose zone is hundreds of feet thick, rendering transitional excavation methods exceedingly costly and ineffective. Delivery of remedial amendments is one of the most challenging and critical aspects for all remedy-based approaches. The conventional approach for delivery is through heterogeneous deep vadose zone environments present hydrologic and geochemical challenges that limit the effectiveness. Because the flow of solution infiltration is dominantly controlled by gravity and suction, injected liquid preferentially percolates through highly permeable pathways, by-passing low-permeability zones that frequently contain the majority of contamination. Moreover, the wetting front can readily mobilize and enhance contaminant transport to the underlying aquifer prior to stabilization. Development of innovative in-situ technologies may be the only means to meet remedial action objectives and long-term stewardship goals. Surfactants can be used to lower the liquid surface tension and create stabile foams, which readily penetrate low permeability zones. Although surfactant foams have been used for subsurface mobilization efforts in the oil and gas industry, thus far the concept of using foams as a delivery mechanism for transporting remedial amendments into deep vadose zone environments to stabilize metal and long-lived radionuclide contaminants has not been explored. Foam flow can be directed by pressure gradients, rather than being dominated by gravity; and foam delivery mechanisms limit the volume of water (< 5% vol.) required for remedy delivery and emplacement, thus mitigating contaminant mobilization. We will present the results of a numerical modeling and integrated laboratory-/intermediate-scale investigation to simulate, develop, demonstrate, and monitor (i.e., advanced geophysical techniques and advanced predictive biomarkers) foam-based delivery of remedial amendments to remediate metals and radionuclides in vadose zone environments.

Functionally, the methods for addressing contamination must remove and/or reduce transport or toxicity of contaminants. This problem is particularly challenging in arid environments where the vadose zone can be up to hundreds of feet thick, rendering transitional excavation methods exceedingly costly and ineffective. Delivery of remedial amendments is one of the most challenging and critical aspects for all remedy-based approaches. The conventional approach for delivery is through injection of aqueous remedial solutions. However, heterogeneous vadose zone environments present hydrologic and geochemical challenges that limit the effectiveness. Because the flow of solution infiltration is dominantly controlled by gravity and suction, injected liquid preferentially percolates through highly permeable pathways, by-passing low-permeability zones which frequently contain the majority of the contamination. Moreover, the wetting front can readily mobilize and enhance contaminant transport to underlying aquifers prior to stabilization. Development of innovative, in-situ technologies may be the only way to meet remedial action objectives and long-term stewardship goals. Shear-thinning fluids (i.e., surfactants) can be used to lower the liquid surface tension and create stabile foams, which readily penetrate low permeability zones. Although surfactant foams have been utilized for subsurface mobilization efforts in the oil and gas industry, so far, the concept of using foams as a delivery mechanism for transporting reactive remedial amendments into deep vadose zone environments to stabilize metal and long-lived radionuclide contaminants has not been explored. Foam flow can be directed by pressure gradients, rather than being dominated by gravity; and, foam delivery mechanisms limit the volume of water (&lt; 20% vol.) required for remedy delivery and emplacement, thus mitigating contaminant mobilization. We will present the results of a numerical modeling and integrated laboratory-/intermediate-scale investigation to simulate, develop, demonstrate, and monitor (i.e. advanced geophysical techniques and advanced predictive microbial markers) foam-based delivery of remedial amendments to remediate metals and radionuclides in vadose zone environments.

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