Iodine effective diffusion coefficients through volcanic rock: Influence of iodine speciation and rock geochemistry.

Accurate prediction of the subsurface transport of iodine species is important for the assessment of long-term nuclear waste repository performance, as well as monitoring compliance with the Comprehensive Nuclear-Test-Ban Treaty, given that radioiodine decays into radioxenon. However, the transport of iodine through intact geologic media is not well understood, compromising our ability to assess risk associated with radioiodine migration. The current study's goal is to quantify the matrix diffusion of iodine species through saturated volcanic rock, with particular attention paid to the redox environment and potential speciation changes. Diffusion experiments were run for iodide through lithophysae-rich lava, lithophysae-poor lava, and welded tuff, whereas iodate diffusion was studied through welded tuff. Iodine transport was compared with a conservative tracer, HDO, and effective diffusion coefficients were calculated. Likely due to a combination of size and anion exclusion effects, iodine species diffused more slowly than the conservative tracer through all rock types tested. Furthermore, oxidation of iodide to iodate was observed in the lithophysae-poor lava, affecting transport. Results provide much needed data for subsurface transport models that predict radioiodine migration from underground sources, and indicate the pressing need for geochemical and redox interactions to be incorporated into these models.

Field experiments of surface water to groundwater recharge to characterize the mobility of uranium and vanadium at a former mill tailing site.

Characterizing the mobility of uranium and vanadium in groundwater with a hydraulic connection to surface water is important to inform the best management practices of former mill tailing sites. In this study, the recharge of river water to the unsaturated and saturated zones of a uranium-contaminated alluvial aquifer was simulated in a series of forced-gradient single- and multi-well injection-extraction tests. The injection fluid (river water) was traced with natural and artificial tracers that included halides, fluorobenzoates, lithium, and naphthalene sulfonate to characterize the potential mass transport mechanisms of uranium and vanadium. The extraction fluid (river water/groundwater mixture) was analyzed for the tracers, uranium, and vanadium. The results from the tracers indicated that matrix diffusion was likely negligible over the spatiotemporal scales of the tests as evident by nearly identical breakthrough curves of the halides and fluorobenzoates. In contrast, the breakthrough curves of lithium and naphthalene sulfonate indicated that sorption by cation exchange and sorption to organic matter, respectively, were potential mass transport mechanisms of uranium and vanadium. Uranium was mobilized in the saturated zone containing gypsum (gypsum-rich zone), the vadose zone (vadose-rich zone), and the saturated zone containing organic carbon (organic-rich zone) whereas vanadium was mobilized only in the saturated gypsum-rich zone. The mechanisms responsible for the mobilization of uranium and vanadium were likely dissolution of uranium- and vanadium-bearing minerals and/or desorption from the gypsum-rich zone, flushing of uranium from the vadose-rich zone, and desorption of uranium from the organic-rich zone due to the natural contrast in the geochemistry between the river water and groundwater. The experimental design of this study was unique in that it employed the use of multiple natural and artificial tracers coupled with a direct injection of native river water to groundwater. These results demonstrated that natural recharge and flooding events at former mill tailing sites can mobilize uranium, and possibly vanadium, and contribute to persistent levels of groundwater contamination.