Iodide interactions with clay minerals: Batch and diffusion studies

Clay minerals are likely candidates to aid in nuclear waste isolation due to their low permeability, favorable swelling properties, and high cation sorption capacities. Iodine-129 is often the major driver of exposure risk from nuclear waste repositories at timescales >10,000 years. Therefore, understanding the geochemical cycling of iodine in clays is critical in developing defensible quantitative descriptions of nuclear waste disposal. Anions are not typically considered to interact with most clays as it is assumed that the fixed negative charge of clays actively repels the dissoloved anion. This is corroborated by many batch studies, but diffusion experiments in compacted clays have shown iodide retardation relative to chloride. The reasons for this are unknown; however, several possible hypotheses include: redox transformation controls on sorption behavior, complex surface charge environments due to overlapping charge domains, and sorption to ancillary minerals or weathering products. Seven different clay minerals have been examined using several techniques to chracterize the surface charge environment and iodide uptake. The use of a series of clays shifts the independent variable away from water chemistry characteristics (pH, contaminant concentration), and toward structural characterisitics of clay minerals including isomorphous substitution and clay texture. Iodide uptake batch experiments were completed with the clay minerals in a range of swamping electrolytes. The results give evidence for a novel uptake mechanism involving ion pair formation and iodide concentration within nano-confined environments. These results were further tested using diffusional columns where nano-confined regimes make up a larger proportion of the total porosity. These columns were compacted to different hydrostatic pressures and saturated with different ionic compositions. Porosity distributions were characterized with a fluoride tracer. Iodide diffusion characteristics were found to be dependent on ionic composition and confining pressure. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corperation, for the U.S. Department of Energy's Nation Nuclear Security Administration under contract DE-AC04-94AL85000.