Kenton A. Rod

Transport of strontium and cesium in simulated Hanford tank waste leachate through quartz sand under saturated and unsaturated flow.

We investigated the effects of water saturation and secondary precipitate formation on Sr and Cs transport through quartz sand columns under saturated and unsaturated flow. Column experiments were conducted at effective water saturation ranging from 0.2 to 1.0 under steady-state flow using either 0.1 M NaNO(3) or simulated tank waste leachate (STWL; 1 M NaNO(3) and 1 M NaOH) mimicking Hanford (Washington, USA) tank waste. In 0.1 M NaNO(3) columns, Sr transported like a conservative tracer, whereas Cs was retarded relative to Sr. The transport of Sr and Cs in the 0.1 M NaNO(3) columns under all water saturations could be described with the equilibrium convection-dispersion equation (CDE). In STWL columns, Sr mobility was significantly reduced compared to the 0.1 M NaNO(3) column, because Sr was incorporated into or sorbed to neo-formed secondary precipitates. Strontium sequestration by precipitates was confirmed by additional batch and electron micrograph analyses. In contrast(,) the transport of Cs was less affected by the STWL; retardation of Cs in STWL columns was similar to that found in 0.1 M NaNO(3) columns. Analysis of STWL column data revealed that both Sr and Cs breakthrough curves showed nonideal behavior that suggest nonequilibrium conditions, although nonlinear geochemical behavior cannot be ruled out.

Strontium and Cesium Release Mechanisms during Unsaturated Flow through Waste-Weathered Hanford Sediments

Leaching behavior of Sr and Cs in the vadose zone of Hanford site (Washington) was studied with laboratory-weathered sediments mimicking realistic conditions beneath the leaking radioactive waste storage tanks. Unsaturated column leaching experiments were conducted using background Hanford pore water focused on first 200 pore volumes. The weathered sediments were prepared by 6 months reaction with a synthetic Hanford tank waste leachate containing Sr and Cs (10(-5) and 10(-3) molal representative of LO- and HI-sediment, respectively) as surrogates for (90)Sr and (137)Cs. The mineral composition of the weathered sediments showed that zeolite (chabazite-type) and feldspathoid (sodalite-type) were the major byproducts but different contents depending on the weathering conditions. Reactive transport modeling indicated that Cs leaching was controlled by ion-exchange, while Sr release was affected primarily by dissolution of the secondary minerals. The later release of K, Al, and Si from the HI-column indicated the additional dissolution of a more crystalline mineral (cancrinite-type). A two-site ion-exchange model successfully simulated the Cs release from the LO-column. However, a three-site ion-exchange model was needed for the HI-column. The study implied that the weathering conditions greatly impact the speciation of the secondary minerals and leaching behavior of sequestrated Sr and Cs.

EMSL Pore Scale Modeling Challenge/Workshop

Report covers the background for the workshop, objectives, important research directions, necessary capabilities and overall recommendations.

Effect of chemical and physical heterogeneities on colloid-facilitated cesium transport

A set of column experiments was conducted to investigate the chemical and physical heterogeneity effect on colloid facilitated transport under slow pore velocity conditions. Pore velocities were kept below 100 cm d-1 for all experiments. Glass beads were packed into columns establishing four different conditions: 1) homogeneous, 2) mixed physical heterogeneity, 3) sequentially layered physical heterogeneity, and 4) chemical heterogeneity. The homogeneous column was packed with glass beads (diameter 500-600 μm), and physical heterogeneities were created by sequential layering or mixing two sizes of glass bead (500-600 μm and 300-400 μm). A chemical heterogeneity was created using 25% of the glass beads coated with hydrophobic molecules (1H-1H-2H-2H-perfluorooctyltrichlorosilane) mixed with 75% pristine glass beads (all 500-600 μm). Input solution with 0.5 mM CsI and 50 mg L-1 colloids (1-μm diameter SiO2) was pulsed into columns under saturated conditions. The physical heterogeneity in the packed glass beads retarded the transport of colloids compared to homogeneous (R = 25.0), but showed only slight differences between sequentially layered (R = 60.7) and mixed heterogeneity(R = 62.4). The column with the chemical, hydrophobic/hydrophilic, heterogeneity removed most of the colloids from the input solution. All column conditions stripped Cs from colloids onto the column matrix of packed glass beads.

Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) vibrational spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized toward defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement-polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG vibrational spectroscopy.