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.

Aging effects on Cesium-137 (137Cs) sorption and transport in association with clay colloids.

Migration of radionuclides via colloid-facilitated transport is an important component of nuclear repository performance models. 137Cs sorption to bentonite colloids follows multi-site behavior, with sorption to weak sites being a rapid process and sorption to strong sites having slow kinetics. Experiments in this study targeted desorption of 137Cs from strong sites on the colloids by placing the 137Cs-bearing colloids in contact with a strongly-sorbing zeolite material that competes with the colloids for 137Cs sorption. Batch and column experiments were conducted to examine the effects of aging (i.e., increased contact time between 137Cs and colloids) on colloid-facilitated transport of 137Cs through crushed analcime columns. A larger proportion of 137Cs-bearing colloids eluted through a series of columns when the colloids were aged for 1200 days prior to injection in comparison to unaged colloids. Aging the colloids increased the partitioning of 137Cs to the colloids by nearly 20% after 1200 h. Slow desorption (0.27 hr-1) from the strong sites resulted in an increase of the Cs fraction bound to the strong sites from 0.365 to 0.87 by the second column injection, resulting in increased colloid-facilitated transport of Cs through strongly-sorbing zeolites from 0 in the second unaged column to 10% in the second aged column.

Comparison of experimental methods for estimating matrix diffusion coefficients for contaminant transport modeling.

Diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating effective matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of effective matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged from 14 to 30%, and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than effective matrix diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields effective matrix diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.

Dispersion stability and electrokinetic properties of intrinsic plutonium colloids: implications for subsurface transport.

Subsurface transport of plutonium (Pu) may be facilitated by the formation of intrinsic Pu colloids. While this colloid-facilitated transport is largely governed by the electrokinetic properties and dispersion stability (resistance to aggregation) of the colloids, reported experimental data is scarce. Here, we quantify the dependence of ζ-potential of intrinsic Pu(IV) colloids on pH and their aggregation rate on ionic strength. Results indicate an isoelectric point of pH 8.6 and a critical coagulation concentration of 0.1 M of 1:1 electrolyte at pH 11.4. The ζ-potential/pH dependence of the Pu(IV) colloids is similar to that of goethite and hematite colloids. Colloid interaction energy calculations using these values reveal an effective Hamaker constant of the intrinsic Pu(IV) colloids in water of 1.85 × 10(-19) J, corresponding to a relative permittivity of 6.21 and refractive index of 2.33, in agreement with first principles calculations. This relatively high Hamaker constant combined with the positive charge of Pu(IV) colloids under typical groundwater aquifer conditions led to two contradicting hypotheses: (a) the Pu(IV) colloids will exhibit significant aggregation and deposition, leading to a negligible subsurface transport or (b) the Pu(IV) colloids will associate with the relatively stable native groundwater colloids, leading to a considerable subsurface transport. Packed column transport experiments supported the second hypothesis.

Matrix diffusion coefficients in volcanic rocks at the Nevada test site: influence of matrix porosity, matrix permeability, and fracture coating minerals.

Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ((3)HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient (D(m)/D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of (D(m)/D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log(D(m)/D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log(D(m)/D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.