DOE OSTI2011
In this exploratory project, we are testing two interrelated hypotheses about the sorption of Cs within weathered micaceous materials in subsurface regolith materials from the Savannah River Site (SRS) located on the Atlantic Coastal Plain: 1) that stable cesium has become significantly enriched relative to potassium in subsurface micaceous particles as a result of chemical weathering processes; and 2) that the Cs so present is sufficient to be a major factor determining the ability of the subsurface materials to take up and hold 137 Cs. To test these hypotheses, we collected by hand augur soil samples corresponding to soils representative at the SRS: upland regolith (Fuquay series); soils formed on Tobacco Road Sandstone; and, soils formed on Quaternary Alluvium. From our data, the quantification of the amounts of stable cesium concentrated in various sites within 2:1 phyllosilicates by natural processes is highly relevant toward understanding the future sorption of 137 Cs by the mica, illite, vermiculite, and hydroxyl interstratified vermiculite (HIV) phases present in the subsurface at and in proximity to SRS. Studying sorption and fixation of Cs in these micaceous phases interlayers potentially leads to increased knowledge to the extent that stable Cs resists exchange with ion exchange cations (Mg, NH4, or even alkyl ammonium compounds) and to the extent that Cs can become fixed over the long term. Such knowledge will help in the development of 137 Cs remediation strategies for the long-term, which is a critical aspect of the SBR goals. We characterized the mineralogy, K-Ar ages of the soil and soil clay fractions (before and after acid treatment), and alkali element chemistry (K, Rb, Cs) of the clay fractions of soils collected from these three different types of soils. The clay fractions of the Fuquay soils are composed of kaolinite, and hydroxy interstratified vermiculite (HIV). Kaolinite, HIV, quartz, gibbsite and illite are found in the quaternary soils. Leach experiments using 10% nitric acid and 50% nitric acid were performed on 62 mesh fractions to show the amounts of Cs and Rb relative to K (Cs/K, Rb/K) that are exchangeable in these soils compared to Coastal Plain micas and upper continental crust. The Cs/K and Rb/K of the leachates are considerably higher relative to both upper continental crust and relative to weathered micas found in Georgia Coast Plain sediments. The K-Ar ages of the clay fractions of five different SRS soil series were ca. 320 Ma. After leaching with nitric acid, the ages of the soil clay fractions were approximately the same as the unleached soil clays. Based on the similarity of these ages to the ages of Coastal Plain micas, the K and Ar remaining after treatment is believed to be enclosed in a relect mica in the HIV phases in the soils. The HIV is likely a mica-HIV intergrade. Based on these data, stable cesium has become significantly enriched relative to potassium in subsurface micaceous particles as a result of chemical weathering processes in the SRS Fuquay soils studied thus far. Our data permit the interpretation describing the sorption of Cs and Rb in an apex site or in a hard to reach hard-to-exchange sorption site during pedogenesis. In terms of testing the second hypothesis, our work is ongoing and we report some preliminary data on Cs-137 and Rb-85 exchange experiments on select SRS Fuquay soils (-2 mm). Our isotopic equilibration experiments using Cs and Rb isotopes in separate exchange experiments show only small amounts of Cs and Rb in the original sample is exchangeable isotopically for a period of a few weeks in acidified conditions. The isotope exchange experiments provide support for our interpretation that pedogenically accumulated Cs (and Rb) occupy sites that are unavailable to exchange or exchange slowly in acid conditions corresponding to present conditions in SRS soils. In more basic solutions, greater exchange isotopic exchange is noted and suggests an expansion of interlayer sites thereby permitting more isotopic exchange of Cs and Rb.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗