Iodide Sorption to Clays and the Relationship to the Surface Charge Environment
Abstract
In performance assessments of nuclear waste repositories, iodine-129 is often the major contributor to dose at time scales ≥10,000 years. The breakthrough behavior of iodine is determined by the monovalent, anionic nature and the assumed lack of surface reactivity of the iodide ion. This assumption is corroborated by batch sorption data where iodide sorption to clays is typically very small, and only measurable under specific conditions. This result is consistent with charge repulsion arguments due to the fixed negative charge of clays repelling the anionic iodide. However, in compacted column diffusion experiments, iodide is routinely retarded relative to tritium, and is described with Kd values from ≈0.001-2.9ml/g. While small, these values can dramatically change the dose profile in performance assessment calculations. We hypothesize that contributions from the basal plane and edge charge of individual clay particles as well as the physical morphology of the clay particles are contributing to the conflicting behavior. In a series of experiments involving a wide range of clay minerals from the clay bank repository, both surface charge and iodide sorption were examined using surface titrations and batch sorption experiments. The clay minerals studied include: kaolinite, ripidolite, illite, montmorillonite, palygorskite, sepiolite, and an illite/smectite mixed layer clay. Each of these clays was characterized using XRD, and surface titrations in 0.01, 0.1, and 0.5 M NaCl electrolyte. The titrations spanned the pH range from 2.5-10.5 and were automated using an autotitrator. For reference, similar titrations were performed on pure forms of an Al-O powder. The titration curves were interpreted using an inversion method to attain the pKa distribution for each clay and metal oxide at each ionic strength. The pKa distribution for the Al-O shows two distinct peaks at 4.8 and 7.5, which are invariant with ionic strength. The pKa distribution of clays was highly variable between the different minerals and, more importantly, the distribution for an individual clay mineral changed as a function of ionic strength. This behavior implies a more complicated vision of clay surface chemistry than traditional surface complexation descriptions allow. Iodide sorption experiments were completed at relatively high solid:solution ratios to exacerbate sorption properties. The results show a range of sorption behaviors across the clay minerals based on solid:solution ratio, pH, and ionic strength. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
- Publication:
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AGU Fall Meeting Abstracts
- Pub Date:
- December 2011
- Bibcode:
- 2011AGUFM.H53I1525M
- Keywords:
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- 0412 BIOGEOSCIENCES / Biogeochemical kinetics and reaction modeling;
- 1000 GEOCHEMISTRY