Shi-Ping Teng

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.

Removal of cesium ions from aqueous solution by adsorption onto local Taiwan laterite

Utilization of local Taiwan laterite (LTL) to remove aqueous cesium was investigated in this work under the conditions of various contact time, cesium (Cs) loading and temperature. Experimental results show that adsorption is instantaneous. Freundlich and Langmuir simulation results demonstrate that local Taiwan laterite has high affinity and sorption capacity for Cs at low temperatures, which may be attributed to enhanced desorption as temperature increased. Thermodynamic parameters including DeltaH, DeltaG and DeltaS were calculated and it is indicated that Cs adsorption on LTL is an exothermic, spontaneous and physical adsorption reaction. Moreover, the adsorbed Cs is distributed evenly on the LTL surface, which is confirmed by SEM/EDS mapping images. Furthermore, the absence of apparent shifting or broadening of the kaolinite signal in XRD patterns after Cs adsorption is an indication of the non-expanding characteristic of kaolinite structure.

Bridging the gap between batch and column experiments: A case study of Cs adsorption on granite.

Both batch and column methods are conventionally utilized to determine some critical parameters for assessing the transport of contaminants of concern. The validity of using these parameters is somewhat confusing, however, since outputs such as distribution coefficient (Kd) from these two approaches are often discrepant. To bridge this gap, all possible factors that might contribute to this discrepancy were thoroughly investigated in this report by a case study of Cs sorption to crushed granite under various conditions. Our results confirm an important finding that solid/liquid (S/L) ratio is the dominant factor responsible for this discrepancy. As long as the S/L ratio exceeds 0.25, a consistent Kd value can be reached by the two methods. Under these conditions (S/L ratios>0.25), the sorption capacity of the solid is about an order of magnitude less than that in low S/L ratios (<0.25). Although low sorption capacity is observed in the cases of high S/L ratios, the sorption usually takes place preferentially on the most favorable (thermodynamically stable) sorption sites to form a stronger binding. This is verified by our desorption experiments in which a linear isotherm feature is shown either in deionized water or in 1M of ammonium acetate solutions. It may be concluded that batch experiment with an S/L ratio exceeding 0.25 is crucial to obtain convincing Kd values for safety assessment of radioactive waste repository.

Effect of Alkyl Properties and Head Groups of Cationic Surfactants on Retention of Cesium by Organoclays

Cationic surfactants modified clays exhibit high sorptive capability toward anionic radionuclides but retention of cationic radionuclides was concurrently reduced. In this study, organoclays were synthesized by intercalating a variety of primary/quaternary alkylammonium species (NH(2)R/(CH(3))(3)N(+)RBr(-), where R = benzyl, dodecyl, and octadecyl) into bentonite MX-80. The effect of surfactants properties on enhancing or limiting cationic sorption capability was investigated by performing Cs sorption experiments. Experimental results were analyzed using the MINEQL+ software by considering Cs uptake by structural and edge sorption sites. Bentonites that were intercalated with primary alkylammonium surfactants had a higher sorptive capacity than those intercalated with quaternary alkylammonium surfactants. Samples intercalated with octadecyl-bearing surfactants had the lowest sorption rate. XRD and FTIR analyses revealed that each organoclay had a characteristic arrangement of alkyl chains. The cation retention of organoclays was dominated by the extent of hydrophobic interactions affected by the local distribution and arrangement of surfactants. The intercalated primary alkylammoniun surfactants tended to transform into local clusters with a high packing density, leaving more structural sites available for Cs uptake. In contrast, the NH(3)R(+)-surfactants tended to form a denser monolayer over clay surface, inhibiting the retention of Cs at structural sites.

Experimental and numerical investigations of effect of column length on retardation factor determination: A case study of cesium transport in crushed granite

This study investigated breakthrough curves (BTCs) from a series of column experiments, including different column lengths and flow rates, of a conservative tracer, tritium oxide (HTO), and a radionuclide, cesium, in crushed granite using a reactive transport model. Results of the short column, with length of 2cm, showed an underestimation of the retardation factor and the corresponding HTO BTCs cannot be successfully modeled even with overestimated fluid dispersivity. Column supporting elements, including filters and rings, on both ends of packed granite were shown to be able to induce additional dispersive mixing, thus significantly affecting BTCs of short columns while those of the long column, with length of 8cm, were less affected. By increasing flow rates from 1mL/min to 5mL/min, the contribution of structural dispersive mixing to the false tilting of short column BTCs still cannot be detached. To reduce the influence of structural dispersivity on BTCs, the equivalent pore volume of column supporting materials should be much smaller than that of packed porous medium. The total length of column supporting structures should be greatly shorter than that of porous medium column.

Desorption of cesium from granite under various aqueous conditions

In this work the desorption of cesium ions from crushed granite in synthetic groundwater (GW) and seawater (SW) was investigated. Results were compared with those obtained in deionized water (DW) and in two kinds of extraction solutions, namely: MgCl(2) and NaOAc (sodium acetate). In general, the desorption rate of Cs from crushed granite increased proportionally with initial Cs loadings. Also, amounts of desorbed Cs ions followed the tendency in the order SW>GW>NaOAc approximately equal MgCl(2)>DW solutions. This indicated that the utilization of extraction reagents for ion exchange will underestimate the Cs desorption behavior. Fitting these experimental data by Langmuir model showed that these extraction reagents have reduced Cs uptake by more than 90%, while only less than 1% of adsorbed Cs ions are still observed in GW and SW solutions in comparison to those in DW. Further SEM/EDS mapping studies clearly demonstrate that these remaining adsorbed Cs ions are at the fracture areas of biotite.

Sorption of cesium on granite under aerobic and anaerobic conditions

This study focused on the determination of distribution coefficients (Kd) of 137Cs under aerobic (∼21% O2) and anaerobic conditions (1−10 ppm O2) which might be found in the deep geologic environment. The anaerobic conditions were simulated in a glove box filled with highly pure argon (99.9%). Both batch tests and solid-phase analyses, including X-ray diffraction, N2-BET surface area, and polar-microscopy/autoradiography were employed for analyzing the sorption of 137Cs on granite, which is the potential host rock for waste disposal in Taiwan. Before starting batch tests, the rock samples were placed in the glove box for one week, and the Eh values of experimental liquids were periodically measured until the Eh value decreased below 0 mV. The sorption of 137Cs was studied at various concentrations in synthetic groundwater. The Freundlich sorption isotherm seems to be adequate to quantitatively describe the sorption of Cs for the concentration ranges (i.e., 10-3−10-6 M) conducted in both conditions. The distribution coefficient (K) obtained from the two-week batch tests indicated no obvious difference in two systems and the values of K and n are similar. In addition, sorption onto a specific host rock was found to be dependent on its mineralogical components. The photos obtained from polar-microscopy/autoradiography analyses showed that biotite is the principal mineral component responsible for the sorption of 137Cs onto granite.

Analysis of I-129 in radwastes by neutron activation

Abstract Determination of 129I activity of low-level waste has become important from the standpoint of radiation safety and environmental concern. The 129I generated from power plants could be released into the environment through the subsequent fuel reprocessing and waste disposal. In order to minimize this impact, the concentrations of 129I and some affiliated radionuclides in the wastes to be disposed of should be determined and put in compliance with the stipulated regulations. In this work, neutron activation analysis is proposed to determine 129I/127I and 129I in radwastes. The long-lived 126I, activated from 127I, is selected to replace 128I as an indicator of stable iodine. Long-term neutron irradiation and γ-ray counting are permitted and the related detection limit can be improved. In addition, the proposed method has related advantages of low-counting interferences and convenience for chemical operation over traditional methods; these make it a practical alternative for analyzing 129I in radwastes in a facility near a research reactor.

The development of a through-diffusion model with a parent-daughter decay chain.

A valid performance assessment of radioactive waste repositories strongly depends on the reliability of nuclide transport parameters, including distribution and diffusion coefficients. To reduce the waste produced and time spent conducting diffusion experiments, a robust model is required to accurately interpret the experiment results. Therefore, we developed a through-diffusion model with parent-daughter nuclide decay chain. We validated our model through comparisons with the Moridis model (Moridis, 1999) and Bharat model (Bharat et al., 2009), assessing our model and these two models using the distribution of parent nuclide concentrations. This strongly supports the rationality and functionality of extending our proposed model to daughter nuclides. In this study, we derived analytical solutions for the parent nuclides of the through-diffusion experiment using the multicompartment (MC) model. We also propose a simplified formula for estimating the apparent diffusion coefficient of parent nuclides based on the analytical solutions. Through numerical experiments, we verified the feasibility of the formula. Our models are useful for determining the apparent diffusion coefficient of daughter nuclides when conducting through-diffusion experiments with parent-daughter nuclide decay chains. Additionally, the proposed models offer the advantages of saving time and reducing experimental waste.

Interactions involving strontium and various organic acids on the surface of bentonite (MX-80)

The adsorption of strontium (Sr) by bentonite in the presence of various dicarboxylic and aromatic acids was investigated. Strontium uptake was strongly influenced by ionic strength, but not by the presence of the organic acids. However, Sr significantly affected the binding of the organic acids. X-ray diffraction (XRD) results suggested that the interlayer spacing of MX-80 bentonite was affected by the presence of Sr, particularly when organic acids were also present. Cation exchange is the major Sr uptake mechanism, and competition with divalent ions should be considered. Thermodynamic modelling and XRD results suggested that surface precipitation of Sr occurs at high pH values.