Antionette T. Owen

Laboratory Testing of Bulk Vitrified and Steam Reformed Low-Activity Waste Forms to Support A Preliminary Risk Assessment for an Integrated Disposal Facility

Laboratory testing was conducted on bulk vitrified and steam reformed waste forms to supply the input parameters needed for reactive chemical transport calculations with the Subsurface Transport Over Reactive Multiphases (STORM) code. This same code was used to conduct the 2001 ILAW performance assessment. The required input parameters for both waste forms are derived from a mechanistic model that describes the effect of solution chemistry on contaminant release rates. The single-pass flow-through test was the principal method used to obtain these input parameters, supplemented by product consistency test measurements and physical property measurements.

Radionuclide-Chelating Agent Complexes in Low-Level Radioactive Decontamination Waste; Stability, Adsorption and Transport Potential

Speciation calculations were done to determine whether organic complexants facilitate transport of radionuclides leached from waste buried in soils. EDTA readily mobilizes divalent transition metals and moderately impacts trivalent actinides. Picolinate readily mobilizes only Ni2+ and Co2+. These speciation predictions ignore the influence of soil adsorption and biodegradation that break apart the complexes. In adsorption studies, picolinate concentrations have to be >10-4 M to lower the adsorption of Ni and Co. For Sm(III), Th(IV), Np(V), U(VI), and Pu, the picolinate concentration must be >10-3 M before adsorption decreases. EDTA forms strong complexes with divalent transition metals and can stop adsorption of Ni and Co when EDTA solution concentrations are 10-5 M. EDTA complexes with Np(V), U(VI), and Pu are much weaker; EDTA concentrations would have to be >10-3 M to adversely effects non-transition metal/radionuclide adsorption. Most picolinate and ETDA-metal complexes appear to readily dissociate during interactions with soils. The enhanced migration of radionuclide-organic complexes may be limited to a few unique conditions. We recommend that mixtures of metal/radionuclides and EDTA should not be solidified or co-disposed with high pH materials such as cement. For weaker binding organic complexants, such as picolinate, citrate and oxalate, co-disposal of decontamination wastes and concrete should be acceptable.

Tc Reductant Chemistry and Crucible Melting Studies with Simulated Hanford Low-Activity Waste

The FY 2003 risk assessment (RA) of bulk vitrification (BV) waste packages used 0.3 wt% of the technetium (Tc) inventory as a leachable salt and found it sufficient to create a significant peak in the groundwater concentration in a 100-meter down-gradient well. Although this peak met regulatory limits, considering uncertainty in the actual Tc salt fraction, peak concentrations could exceed the maximum concentration limit (MCL) under some scenarios so reducing the leachable salt inventory is desirable. The main objective of this study was to reduce the mobile Tc species available within a BV disposal package by reducing the oxidation state of the Tc in the waste feed and/or during melting because Tc in its reduced form of Tc(IV) has a much lower volatility than Tc(VII). Reduced Tc volatility has a secondary benefit of increasing the Tc retention in glass.

Glass/Ceramic Interactions in the Can-In-Canister Configuration for Disposal of Excess Weapons Plutonium

A can-in-canister waste package design has been proposed for disposal of pyrochlore rich ceramics containing excess weapons plutonium. The can-in-canister configuration consists of a high-level waste (HLW) canister fitted with a rack that holds minicanisters containing the ceramic. The HLW canister is then filled with glass. The pressurized unsaturated flow (PUF) technique was used to investigate waste form/waste form interactions that may occur when water penetrates the waste containers and contacts the waste forms. Volumetric water content was observed to increase steadily from accumulation of water mass as waters of hydration associated with alteration phases formed on the glass surface. Periodic excursions in effluent electrical conductivity and pH were monitored and correlated with secondary phases formed during the test. Plutonium exited the PUF system primarily as filterable particulates. However, effluent Pu and Gd concentrations were found to decrease with time and remained at near detection limits after approximately 250 days, except during transient pH excursions. These results indicate that both Pu and Gd will be retained in the can-in-canister waste package to a very high degree.

HLW Glass Studies: Development of Crystal-Tolerant HLW Glasses

In our study, a series of lab-scale crucible tests were performed on designed glasses of different compositions to further investigate and simulate the effect of Cr, Ni, Fe, Al, Li, and RuO2 on the accumulation rate of spinel crystals in the glass discharge riser of the HLW melter. The experimental data were used to expand the compositional region covered by an empirical model developed previously (Matyas et al. 2010b), improving its predictive performance. We also investigated the mechanism for agglomeration of particles and impact of agglomerates on accumulation rate. In addition, the TL was measured as a function of temperature and composition.