Mikazu Yui

An integrated sorption-diffusion model for the calculation of consistent distribution and diffusion coefficients in compacted bentonite

A thermodynamic sorption model and a diffusion model based on electric double layer (EDL) theory are integrated to yield a surface chemical model that treats porewater chemistry, surface reactions, and the influence of charged pore walls on diffusing ions in a consistent fashion. The relative contribution of Stern and diffuse layer to the compensation of the permanent surface charge represents a key parameter; it is optimized for the diffusion of Cs in Kunipia-F bentonite, at a dry density of 400 kg/m3. The model is then directly used to predict apparent diffusivities (Da) of Cs, Sr, Cl-, I- and TcO4- and corresponding distribution coefficients (Kd) of Cs and Sr in different bentonites as a function of dry density, without any further adjustment of surface chemical and EDL parameters. Effective diffusivities (De) for Cs, HTO, and TcO4- are also calculated. All calculated values (Da, De, Kd) are fully consistent with each other. A comparison with published, measured data shows that the present model allows a good prediction and consistent explanation of (i) apparent and effective diffusivities for cations, anions, and neutral species in compacted bentonite, and of (ii) Kd values in batch and compacted systems.

Solubility and Solubility Product at 22°C of UO2(c) Precipitated from Aqueous U(IV) Solutions

Solubility studies on UO2(c), precipitated at 90°C from low-pH U(IV) solutions, were conducted under rigidly controlled redox conditions maintained by EuCl2 as a function of pH and from the oversaturation direction. Samples were equilibrated for 24 days at 90°C and then for 1 day at 22°C. X-ray diffraction (XRD) analyses of the solid phases, along with the observed solubility behavior, identified UO2(c) as the dominant phase at pH≳1.2 and UO2(am) as the dominant phase at pH≳1.2. The UV-Vis-NIR spectra of the aqueous phases showed that aqueous uranium was present in the tetravalent state. Our ability to effectively maintain uranium in the tetravalent state during experiments and the recent availability of reliable values of Pitzer ion-interactionparameters for this system have helped to set reliable upper limits for the log Ko value of ≤ −60.2 + 0.24 for the UO2(c) solubility [UO2(c) + 2H2O ⇌ U4+ + 4OH−] and of >−11.6 for the formation of U(OH)4(aq) [U4++ 4H2O ⇌ U(OH)4(aq) + 4H+]

Reductive dissolution of PuO2(am): The effect of Fe(II) and hydroquinone

PuO2(am) solubility was investigated as a function of time, for pH from 0.5 to 11, and in the presence of 0.001 M FeCl2 or 0.00052 M hydroquinone to determine the effect of environmentally important reducing agents on PuO2(am) solubilization under geological conditions. Equilibrium was reached in <4 days. The observed PuO2(am) solubilities were many orders of magnitude higher than the Pu(IV) concentrations predicted from thermodynamic data. Spectroscopic, solvent extraction, and thermodynamic analyses of data showed that Pu(III) was the dominant aqueous oxidation state. The experimental pH, pe, and Pu(III) concentrations from both the Fe(II) and hydroquinone systems provided a log K0 value of 15.5 ± 0.7 for [PuO2(am) + 4H+ + e− ⇌ Pu3+ + 2H2O]. The data show that reduction reactions involving Fe(II) and hydroquinone are relatively rapid and that reductive dissolution of PuO2(am), hitherto ignored, may play an important role in controlling Pu behavior under reducing environmental conditions.

Experimental and modeling studies on sorption and diffusion of radium in bentonite.

The sorption and desorption behavior of radium on bentonite and purified smectite was investigated as a function of pH, ionic strength and liquid to solid ratio by batch experiments. The distribution coefficients (Kd) were in the range of 10(2) to > 10(4) ml g-1 and depended on ionic strength and pH. Most of sorbed Ra was desorbed by 1 M KCl. The results for purified smectite indicated that Ra sorption is dominated by ion exchange at layer sites of smectite, and surface complexation at edge sites may increase Ra sorption at higher pH region. Reaction parameters between Ra and smectite were determined based on an interaction model between smectite and groundwater. The reaction parameters were then used to explain the results of bentonite by considering dissolution and precipitation of minerals and soluble impurities. The dependencies of experimental Kd values on pH, ionic strength and liquid to solid ratio were qualitatively explained by the model. The modeling result for bentonite indicated that sorption of Ra on bentonite is dominated by ion exchange with smectite. The observed pH dependency was caused by changes of Ca concentration arising from dissolution and precipitation of calcite. Diffusion behavior of Ra in bentonite was also investigated as a function of dry density and ionic strength. The apparent diffusion coefficients (Da) obtained in compacted bentonite were in the range of 1.1 x 10(-11) to 2.2 x 10(-12) m2 s-1 and decreased with increasing in dry density and ionic strength. The Kd values obtained by measured effective diffusion coefficient (De) and modeled De were consistent with those by the sorption model in a deviation within one order of magnitude.

Sensitivity analysis of radionuclide migration in compacted bentonite: a mechanistic model approach.

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength.

Thermodynamic model for the solubility of NdPO4(c) in the aqueous Na+-H+-H2PO4–HPO42–OH–Cl–H2O system

The solubility of NdPO4(c) was studied at 23±2 °C from both the over and undersaturation directions, with pH ranging from 0 to 9, P concentrations ranging from 0.0003 to 1.00M, and equilibration periods ranging from 6 to 57 days. Equilibrium was reached in <6 days. From the H+, Nd, and P concentrations in equilibrated solutions, the logarithm of the thermodynamic equilibrium constant for the reaction (NdPO4(c) ⇄ Nd3++PO43-) was calculated to be -24.65±0.23 and the value of the Pitzer ion-interaction parameter β(2)for Nd3+-H2PO4- was determined to be -92.9. Predictions based on these thermodynamic quantities were in excellent agreement with the experimental data.

Experimental studies on the interaction of groundwater with bentonite

Interactions of sodium bentonite with distilled water and two types of synthetic groundwater were studied by batch experiments. In the experiments, clay and pure minerals were reacted at room temperature under aerobic and anaerobic condition as a function of time and liquid/solid ratio. The clay and pure minerals used in the experiments were Kunigel-V1 (crude Na-bentonite), Kunipia F (purified Na-bentonite), purified Na-smectite (purified from Kunipia F), calcite and pyrite as accessory minerals. The chemical composition in the liquid phase was analyzed through centrifugation and ultrafiltration. Alteration of the distribution of exchangeable cation in the bentonite was analyzed by NH{sub 4}Ac and XRD. The results indicated that the interaction between bentonite (Kunigel-V1) and groundwater under aerobic condition was described by ion exchange reaction of smectite, dissolution of calcite and oxidation of pyrite. From these experimental studies, the model of the interaction of groundwater with bentonite proposed by Wanner was modified. The comparison between calculation and experimental results showed good agreement and indicated that this model could be adopted to predict porewater chemistry of bentonite for performance assessment of geological isolation system of high level waste.

A plutonium geochemical database for performance analysis of high-level radioactive waste repositories

A thermodynamic database (TDB) and a sorption database (SDB) for Pu have been developed in the context of the performance analysis for a high-level radioactive waste (HLW) repository in Japan. The TDB for Pu was based on inputs by international experts. The selected thermodynamic data for Pu are based on reliable measurement data and on a thermodynamic model for Pu(IV) and Pu(VI) and by chemical analogy for Pu(III) and Pu(V). The available ion-interaction parameters are also compiled, especially for Pu(IV) and Pu(III). The finally agreed TDB was used to set the necessary Pu solubility and speciation information for the possible repository conditions. The sorption database for Pu was compiled via extensive literature searches. Data relating to reducing conditions were found to be scarce with the exception of some recent studies. Kd selection was carried out differently for the engineered barrier system (by diffusion studies) and for the geosphere (from the batch SDB).

Applicability of Thermodynamic Database of Radioactive Elements Developed for the Japanese Performance Assessment of HLW Repository

In 1999 Japan Nuclear Cycle Development Institute (JNC) published a second progress report (also known as H12 report) on high-level radioactive waste (HLW) disposal in Japan (JNC 1999). This report helped to develop confidence in the selected HLW disposal system and to establish the implementation body in 2000 for the disposal of HLW. JNC developed an in-house thermodynamic database for radioactive elements for performance analysis of the engineered barrier system (EBS) and the geosphere for H12 report. This paper briefly presents the status of the JNCs thermodynamic database and its applicability to perform realistic analyses of the solubilities of radioactive elements, evolution of solubility-limiting solid phases, predictions of the redox state of Pu in the neutral pH range under reducing conditions, and to estimate solubilities of radioactive elements in cementitious conditions.

Experimental and Numerical Studies on Colloid-Enhanced Radionuclide Transport - The Effect of Kinetic Radionuclide Sorption onto Colloidal Particles -

Numerous studies have shown that colloidal particles in groundwater can facilitate radionuclide transport in subsurface environments. A series of laboratory experiments was conducted to investigate the effects of radionuclide sorption onto colloids and the surfaces of rock fractures. This research especially focused on the kinetic behavior of the sorption process. A mixed solution of Cs and clay colloids was injected into a single artificial fracture in a granite column. Simulations were also performed to analyze the experimental results using a numerical code, COLFRAC, which describes colloid-facilitated solute transport in discretely-fractured media. The code allows for either equilibrium or kinetic sorption onto the colloidal particles. The experimental and analytical results indicate that transport of Cs is facilitated by the colloidal particles, which can sorb Cs and transport through the fracture. The analyses also illustrate the importance of evaluating parameters that describe kinetic sorption onto colloids. Furthermore, radionuclide transport is likely to be retarded as colloidal particles that sorb radionuclides are filtered on the fracture surface.