Engineering topics
Kaplan, D
Publications and source records attributed to Kaplan, D.
Progress on a Cavity with Beryllium Walls for Muon Ionization Cooling Channel R and D
N/A
MOBILIZATION AND CHARACTERIZATION OF COLLOIDS GENERATED FROM CEMENT LEACHATES MOVING THROUGH A SRS SANDY SEDIMENT
Naturally occurring mobile colloids are ubiquitous and are involved in many important processes in the subsurface zone. For example, colloid generation and subsequent mobilization represent a possible mechanism for the transport of contaminants including radionuclides in the subsurface environments. For colloid-facilitated transport to be significant, three criteria must be met: (1) colloids must be generated; (2) contaminants must associate with the colloids preferentially to the immobile solid phase (aquifer); and (3) colloids must be transported through the groundwater or in subsurface environments - once these colloids start moving they become 'mobile colloids'. Although some experimental investigations of particle release in natural porous media have been conducted, the detailed mechanisms of release and re-deposition of colloidal particles within natural porous media are poorly understood. Even though this vector of transport is known, the extent of its importance is not known yet. Colloid-facilitated transport of trace radionuclides has been observed in the field, thus demonstrating a possible radiological risk associated with the colloids. The objective of this study was to determine if cementitious leachate would promote the in situ mobilization of natural colloidal particles from a SRS sandy sediment. The intent was to determine whether cementitious surface or subsurface structure would create plumes that could produce conditions conducive to sediment dispersion and mobile colloid generation. Column studies were conducted and the cation chemistries of influents and effluents were analyzed by ICP-OES, while the mobilized colloids were characterized using XRD, SEM, EDX, PSD and Zeta potential. The mobilization mechanisms of colloids in a SRS sandy sediment by cement leachates were studied.
DISTRIBUTION COEFICIENTS (KD) GENERATED FROM A CORE SAMPLE COLLECTED FROM THE SALTSTONE DISPOSAL FACILITY
Core samples originating from Vault 4, Cell E of the Saltstone Disposal Facility (SDF) were collected in September of 2008 (Hansen and Crawford 2009, Smith 2008) and sent to SRNL to measure chemical and physical properties of the material including visual uniformity, mineralogy, microstructure, density, porosity, distribution coefficients (K{sub d}), and chemical composition. Some data from these experiments have been reported (Cozzi and Duncan 2010). In this study, leaching experiments were conducted with a single core sample under conditions that are representative of saltstone performance. In separate experiments, reducing and oxidizing environments were targeted to obtain solubility and Kd values from the measurable species identified in the solid and aqueous leachate. This study was designed to provide insight into how readily species immobilized in saltstone will leach from the saltstone under oxidizing conditions simulating the edge of a saltstone monolith and under reducing conditions, targeting conditions within the saltstone monolith. Core samples were taken from saltstone poured in December of 2007 giving a cure time of nine months in the cell and a total of thirty months before leaching experiments began in June 2010. The saltstone from Vault 4, Cell E is comprised of blast furnace slag, class F fly ash, portland cement, and Deliquification, Dissolution, and Adjustment (DDA) Batch 2 salt solution. The salt solution was previously analyzed from a sample of Tank 50 salt solution and characterized in the 4QCY07 Waste Acceptance Criteria (WAC) report (Zeigler and Bibler 2009). Subsequent to Tank 50 analysis, additional solution was added to the tank solution from the Effluent Treatment Project as well as from inleakage from Tank 50 pump bearings (Cozzi and Duncan 2010). Core samples were taken from three locations and at three depths at each location using a two-inch diameter concrete coring bit (1-1, 1-2, 1-3; 2-1, 2-2, 2-3; 3-1, 3-2, 3-3) (Hansen and Crawford 2009). Leaching experiments were conducted with a section of core sample 3-2. All cores from location 3 were drilled without using water. Core sample 3-2 was drilled from approximately six inches to a depth of approximately 13 inches. Approximately six inches of the core was removed but it broke into two pieces during removal from the bit. At the time of drilling, core material appeared olive green in color (Smith 2008). The fact that the samples were cored as olive green and were received after storage with a gray outer layer is indicative that some oxidation had occurred prior to leaching studies.
LONG-TERM TECHNETIUM INTERACTIONS WITH REDUCING CEMENTITIOUS MATERIALS
Technetium is among the key risk drivers at the Saltstone Facility. The way that it is immobilized in this cementitious waste form is by converting its highly mobile Tc(VII) form to a much less mobile Tc(IV) form through reduction by the cement's blast furnace slag. This report includes a review of published data and experimental results dealing with Tc leaching from Portland cement waste forms. The objectives for the literature study were to document previous reports of Tc interactions with slag-containing cementitious materials. The objectives for the laboratory study were to measure Tc-saltstone Kd values under reducing conditions. From the literature it was concluded: (1) Spectroscopic evidence showed that when Tc(IV) in a slag-cement was exposed to an oxidizing environment, it will convert to the more mobile Tc(VII) species within a short time frame, 2.5 years. (2) SRS saltstone will reduce Tc(VII) in the absence of NaS or sodium dithionite in a reducing atmosphere. (3) Only trace concentrations of atmospheric oxygen (30 to 60 ppm O{sub 2}; Eh 120 mV) at the high pH levels of cementitious systems is required to maintain Tc as Tc(VII). (4) Experimental conditions must be responsible for wide variability of measured K{sub d} values, such that they are either very low, {approx}1 mL/g, or they are very high {approx}1000 mL/g, suggesting that Tc(VII) or Tc(IV) dominate the systems. Much of this variability appears to be the result of experimental conditions, especially direct controls of oxygen contact with the sample. (5) A field study conducted at SRS in the 1980s indicated that a slag-saltstone immobilized Tc for 2.5 years. Below background concentrations of Tc leached out of the slag-containing saltstone, whereas Tc leached out of the slag-free saltstone at the rate of nitrate loss. One possible explanation for the immobilization of Tc in this study was that the slag-saltstone maintained reducing conditions within the core of the 55-gallon sample, whereas in the small-scale lab experiments, where samples were crushed to <1mm, oxygen diffused through the particles and reoxidize the slag during the contact period. (6) Present site specific reduction capacity value of 820 {micro}eq/g is in the realm of literature values that were either measured or theoretically estimated based on thermodynamic calculations. (7) Almond and Kaplan (2011) measured desorption K{sub d} values from a Vault 4 saltstone core sample. Desorption leaching tests were conducted in a glovebag maintained at 30 to 60 ppm O2. A ground olive-colored saltstone sample, as compared to black monolith sample, was used in this study, indicating the sample had been exposed to O2, which is likely the cause for the lower then anticipated Kd value measured, 139 mL/g. Tc adsorption experiments were conducted under reducing conditions (<0.5 ppm O{sub 2}(g) -585 mV, 2% H{sub 2}, pH 11.66) and obtained K{sub d} values of {approx}1000 mL/g in a saltstone formulated with 45% slag (nominal concentration) and a K{sub d} of 10,000 mL/g when the saltstone contained 95% slag. The K{sub d} values logarithmically increased from 1 day to 56 days, with little sorption generally occurring in the first eight days. Steady state had not been achieved during the initial 56 days. However, the slag-free cement control samples also had K{sub d} values near 1000 mL/g and extremely low redox conditions, due to the 2% H{sub 2} atmosphere. A key concept that this literature review and the experimental results provide is that Tc immobilization is dependent on experimental conditions, specifically, the available oxygen that can oxidize technetium in a portland cement or saltstone-like monolith. The shrinking core model used in the saltstone performance assessment describes the existence of an oxidized outer layer of concrete surrounding a shrinking core of reducing intact saltstone. A sharp boundary between the two zones moves slowly inward, resulting in oxidation of Tc(IV). This work largely reinforced our conceptual model of the shrinking core model, but more importantly provided clarity regarding process kinetics, mechanisms, and input values for future detailed modeling. The shrinking core model in itself is devoid of geochemical mechanisms. This study provided more geochemical detail to this conceptual numerical model.