An Improved Speciation Method Combining IC with ICPOES and Its Application to Iodide and Iodate Diffusion Behavior in Compacted Bentonite Clay.

An accurate and effective method combining ion chromatography (IC) and inductively coupled plasma optical emission spectrometry (ICP-OES) was applied in this work to qualitatively and quantitatively analyze individual and co-existing iodide (I-) and iodate (IO3-) at various concentrations. More specifically, a very strong linear relationship for the peak area for the co-existing I- and IO3- ions was reached, and a high resolution value between two peaks was observed, which proves the effectiveness of our combined IC-ICP-OES method at analyzing iodine species. We observed lower accessible porosity for the diffusion of both I- and IO3- in samples of bentonite clay using IC-ICP-OES detection methods, where the effective diffusion coefficient varied based on the anion exclusion effect and the size of the diffusing molecules. In fact, the distribution coefficients (Kd) of both I- and IO3- were close to 0, which indicates that there was no adsorption on bentonite clay. This finding can be explained by the fact that no change in speciation took place during the diffusion of I- and IO3- ions in bentonite clay. Our IC-ICP-OES method can be used to estimate the diffusion coefficients of various iodine species in natural environments.

An EXAFS study for characterizing the time-dependent adsorption of cesium on bentonite.

Bentonite is considered for use as a buffer material in the final disposal repositories of radioactive waste. Long-lived 135Cs with a half-life of 2.3 × 106 years is a key radionuclide in high-level waste, and lots of 137Cs with a half-life of 30.2 years exists in low-level waste. Therefore, the adsorption of Cs on bentonite is a critical issue in evaluating the long-term safety of radioactive waste disposal. In this study, EXAFS techniques were used to characterize the time-dependent process from the beginning of adsorption to equilibrium. From the results of this study, we found changes including to the Cs adsorption sites, the Cs-O distance between Cs and the oxygen atom, and that the adsorption of Cs ions occurred before the reaction reached equilibrium. The fraction of OS complexes when Cs was adsorbed on bentonite can refer to the CN (Cs-O1st)/CN (Cs-O2nd) ratio of coordination numbers, and this study found that the OS complex was the major adsorption species when Cs adsorbed onto bentonite. In addition to the ratio CN (Cs-O1st)/CN (Cs-O2nd) providing information on the adsorption site, we also discussed the change of Cs-O1st and Cs-O2nd bond distances to identify the adsorption sites at different times. Comparing the XRD patterns of montmorillonite and bentonite, we found that the interlayer collapsed after Cs was adsorbed onto montmorillonite, but it expanded after Cs was adsorbed onto bentonite. From the results of EXAFS fitting, we found that the movement of Cs ions was from regular interlayer sites to expanded interlayer sites, which caused the interatomic distance of Cs-O2nd to decrease with an increase in time. It was revealed that the adsorption of Cs on bentonite occurred in two steps. The first step includes the rapid uptake of Cs by attachment to the oxygen atoms of the H2O molecules at the regular interlayer sites, especially for the OS complexes. The second step includes a slower process where dehydrated Cs ions move from the regular interlayer sites to the expanded interlayer sites. In this study, Cs L3-edge EXAFS spectroscopy was conducted for the Cs adsorbed on bentonite to identify the Cs adsorption sites over time, as this is important in evaluating the mobility of Cs in the environment. These results are beneficial in finding the process of Cs adsorption on bentonite, which could be used for the design of the final disposal of spent nuclear fuel.

Novel method for analyzing transport parameters in through-diffusion tests.

Buffer materials such as bentonite are vital for absorbing radionuclide leakage and retarding migration from radioactive waste canisters. The diffusion coefficient and the retardation factor are the predominant properties controlling the diffusion-reaction process in a buffer material. Diffusion experiments combined with Crank's graphical method are a well-established process for determining asymptotic diffusion coefficients. However, the inaccuracy of the diffusion coefficient that results from the subjective judgement of the late-time linear part of the cumulative concentration data in Crank's graphical method will deteriorate the estimate of the retardation factor. A novel parameter identification process based on an iterative and analytical method (PIPIAM) is proposed here to obtain the diffusion coefficients and porosity of bentonite using concentration data. The results of PIPIAM and the graphical method are compared through an error analysis of concentration. The results show that PIPIAM outperforms the graphical method in terms of the error reduction of the concentration and the uncertainty decrease of the estimated parameters. The proposed method is thus a good alternative for acquiring transport parameters for use in safety assessments of nuclear waste repositories.

Cesium adsorption and distribution onto crushed granite under different physicochemical conditions.

The adsorption of cesium onto crushed granite was investigated under different physicochemical conditions including contact time, Cs loading, ionic strength and temperature. In addition, the distribution of adsorbed Cs was examined by X-ray diffraction (XRD) and EDS mapping techniques. The results showed that Cs adsorption to crushed granite behaved as a first-order reaction with nice regression coefficients (R(2) > or = 0.971). Both Freundlich and Langmuir models were applicable to describe the adsorption. The maximum sorption capacity determined by Langmuir model was 80 micromol g(-1) at 25 degrees C and 10 micromol g(-1) at 55 degrees C. The reduced sorption capacity at high temperature was related to the partial enhancement of desorption from granite surface. In general, Cs adsorption was exothermic (DeltaH<0, with median of -12 kJ mol(-1)) and spontaneous (DeltaG<0, with median of -6.1 at 25 degrees C and -5.0 kJ mol(-1) at 55 degrees C). The presence of competing cations such as sodium and potassium ions in synthetic groundwater significantly reduces the Cs adsorption onto granite. The scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM/EDS) mapping method provided substantial evidences that micaceous minerals (biotite in this case) dominate Cs adsorption. These adsorbed Cs ions were notably distributed onto the frayed edges of biotite minerals. More importantly, the locations of these adsorbed Cs were coincided with the potassium depletion area, implying the displacement of K by Cs adsorption. Further XRD patterns displayed a decreased intensity of signal of biotite as the Cs loading increased, revealing that the interlayer space of biotite was affected by Cs adsorption.

Adsorption of Se species on crushed granite: a direct linkage with its internal iron-related minerals.

The adsorption of selenium species on crushed granite is investigated directly linking to its internal iron-related minerals. Experimental results demonstrated that granite has higher affinity toward Se(IV) adsorption than Se(VI) adsorption. Se(IV) adsorption on granite is insensitive to background electrolytes while the effect of ionic strength on Se(VI) adsorption is not observed, which is attributed to the overloading of Se(VI) ions. Results of chemical sequential extraction showed that the removal of crystalline iron oxides dramatically reduces Se(IV) adsorption, which corresponds to the disappearance of goethite signal within XRD pattern. Based on our results, it is proposed that goethite within granite dominates Se adsorption in crushed granite. Although these goethites probably stem from some sample preparation processes including drilling in situ, crushing, washing and drying granite samples in laboratory, the formation of goethite enhances the granite affinity toward Se species adsorption. Images of SEM/EDS furthermore revealed that goethite is embedded within the fractures. In addition, quantification by standard addition method by spiking goethite suspension indicates that only around 20% of goethite minerals are available during Se(IV) adsorption.

Evaluation of buffer materials by associating engineering and sorption properties.

To provide an overall functional evaluation of buffer materials, this study attempted to investigate the relationships among the engineering properties, plastic index (PI), compaction efficiency, sorption properties, and distribution ratio (Rd) for some buffer materials composed of quartz sand and bentonite. Th and U were nuclides of interest, and both synthetic groundwater (GW) and seawater (SW) were used for batch sorption experiments, while the deionized water (DIW) was used for engineering property tests. SW and GW were also used to evaluate the effects on PI. The results show that the maximum dry density was reached when bentonite content was 30% with the same compaction energy by the ASTM D698 method. PI and bentonite content of tested buffer materials consisting of bentonite and quartz sand demonstrated a linearly proportional relationship regardless of the solution used. The following sequence of PIDIW > PIGW > PISW is due to coagulation and flocculation effects. The buffer materials of lower PI value could decrease swelling potential and increase permeability. The Rd observed in GW and SW of U increased linearly with PI measured in DIW, although the Rd of Th remained relatively constant above a PI of 88. From the viewpoints of associated engineering and sorption properties, the buffer materials containing 30-50% bentonite are probably the most favorable choice. Another result shows that U has a better additivity with respect to Rd than Th in both synthetic GW and synthetic SW. These results will allow a determination of more effective buffer material composition, and improved estimates of the overall Rd of the buffer material mixture from the Rd of each mineral component.