Performance of the Fluidized Bed Steam Reforming product under hydraulically unsaturated conditions.

Several candidates for supplemental low-activity waste (LAW) immobilization at the Hanford site in Washington State, USA are being considered. One waste sequestering technology considered is Fluidized Bed Steam Reforming (FBSR). The granular product resulting from the FBSR process is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals with a 1:1:1 molar ratio of Na, Al and Si. To demonstrate the durability of the product, which can be disposed of at the unsaturated Integrated Disposal Facility (IDF) at Hanford, a series of tests has been performed using the Pressurized Unsaturated Flow (PUF) system, which allows for the accelerated weathering of the solid materials. The system maintains hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that will be present at the IDF. Two materials were tested using the system: 1) the FBSR granular product and 2) the FBSR granular product encapsulated in a geopolymer to form a monolith. Results of the experiments show a trend of relatively constant effluent concentration of Na, Si, Al, and Cs as a function of time from both materials. The elements I and Re show a steady release throughout the yearlong test from the granular material but their concentrations seem to be increasing at one year from the monolith material. This result suggests that these two elements may be present in the sodalite cage structure rather than in the predominant nepheline phase because their release occurs at a different rate compared to nepheline phase. Also, these elements to not seem to reprecipitate when released from the starting material. Calculated one-year release rates for Si are on the order of 10(-6) g/(m(2) d) for the granular material and 10(-5) g/(m(2) d) for the monolith material while Re release is seen to be two orders of magnitude higher than Si release rates. SEM imaging and XRD analysis show how the alteration of the two materials is dependent on their depth in the column. This phenomenom is a result of depth-dependent solution concentrations giving rise chemical environments that may be supersaturated with respect to a number of mineral phases.

Uranium phases in contaminated sediments below Hanford's U tank farm.

Macroscopic and spectroscopic investigations (XAFS, XRF, and TRLIF) on Hanford contaminated vadose zone sediments from the U-tank farm showed that U(VI) exists as different surface phases as a function of depth below ground surface (bgs). Secondary precipitates of U(VI) silicate precipitates (boltwoodite and uranophane) were present dominantly in shallow-depth sediments (15-16 m bgs), while adsorbed U(VI) phases and polynuclear U(VI) surface precipitates were considered to dominate in intermediate-depth sediments (20-25 m bgs). Only natural uranium was observed in the deeper sediments (> 28 m bgs) with no signs of contact with tank wastes containing Hanford-derived U(VI). Across all depths, most of the U(VI) was preferentially associated with the silt and clay size fractions of sediments. Strong correlation between U(VI) and Ca was found in the shallow-depth sediments, especially for the precipitated U(VI) silicates. Because U(VI) silicate precipitates dominate in the shallow-depth sediments, the released U(VI) concentration by macroscopic (bi)carbonate leaching resulted from both desorption and dissolution processes. Having different U(VI) surface phases in the Hanford contaminated sediments indicates that the U(VI) release mechanism could be complicated and that detailed characterization of the sediments using several different methods would be needed to estimate U(VI) fate and transport correctly in the vadose zone.