Effects of synthetic site water on bentonite-concrete system for a potential nuclear waste repository

In high-level nuclear waste(HLW)repositories,concrete and compacted bentonite are designed to be employed as buffer materials,which may raise a problem of interactions between concrete and bentonite.These interactions would lead to mineralogy transformation and buffer performance decay of bentonite under the near field environment conditions in a repository.A small-scale experimental setup was established to simulate the concrete-bentonite-site water interaction system from a potential nuclear waste repository in China.Three types of mortars were prepared to correspond to the concrete at different degradation states.The results permit the determination of the following:(1)The macroproperties of Gaomiaozi(GMZ)bentonite(e.g.swelling pressure,permeability,the final dry density,and water content of reacted samples);(2)The composition evolution of fluids from the synthetic site water-concrete-bentonite interaction systems;(3)The sample characterization including Fourier transform infrared spectroscopy(FTIR)and X-ray powder diffraction(XRD).Under the infiltration of the synthesis Beishan site water(BSW),the swelling pressure of bentonite decreases slowly with time after reaching its second swelling peak.The flux decreases with time during the infiltrations,and it tends to be stable after more than 120 d.Due to the cation exchange reactions in the BSW-concrete-bentonite systems,the divalent cations(Ca and Mg)were consumed,and the monovalent cations(Na and K)were released.The dissolution of minerals in the bentonite such as albite causes Si increasing in the pore water.It was concluded that the hydro-mechanical property degradation of bentonite takes place when it comes into contact with concrete mortar,even under low-pH groundwater conditions.The soil dispersion,the uneven water content,and the uneven dry density in bentonite samples may partly contribute to the swelling decay of bentonite.Therefore,the direct contact with concrete has an obvious effect on the performance of bentonite.

Performance characteristics of EZhou bentonite of Hubei province and its modification

Both the chemical compositions and performance characteristics of the bentonite raw ores in Ezhou area of Hubei province and Honghuoshan area of Liaoning of these two kinds of bentonites were tested before and province were compared and analyzed. The properties after Na^＋- and Li^＋-modification. The results show that the Ezhou bentonite ore possesses higher montmorillonite content than the Honghuoshan bentonite ore, but the Ezhou Na-bentonite has weaker castability （e.g. wet compression strength and hot wet tensile strength） than the Honghuoshan Na-bentonite, while the performance of Ezhou Li-bentonite, such as colloid index, swelling value, swelling volume and mould coating performance, is equivalent to that of the Honghuoshan Na-bentonite.

Shear resistance of assembled bentonite interface after confined water saturation and interfacial self-healing capacity

The requisite functions of a bentonite buffer in a deep geological repository depend on the sealing/healing of bentonite interfaces,with particular emphasis on the self-healing(automatic healing upon wetting)of assembled bentonite-bentonite interfaces.This study determined the shear resistance(including the peak shear strength and secant modulus)of densely compacted Gaomiaozi(GMZ)bentonite and its assembled interface after confined water saturation.The effect of bentonite dry density and saturation time on the shear resistance of saturated healed interfaces was elucidated,and the interfacial self-healing capacity was assessed.The results indicate that the shear resistance of the saturated healed interfaces increased with the bentonite dry density but had a non-monotonic correlation with the saturation time.For a given dry density of the bentonite,the saturated healed interface exhibits a lower peak shear strength than the saturated intact bentonite but a higher peak shear strength than the saturated separated interface.The saturated healed and separated interfaces have comparable shear moduli(secant moduli),which are lower than that of the saturated intact bentonite.The saturated healed interfaces display smooth shear failure planes,while the saturated assembled interfaces and intact bentonite exhibit comparable frictional angles.This indicates that interfacial self-healing plays a pivotal role in enhancing interfacial peak shear strength by facilitating microstructural bonding at the assembled interface.Finally,it can be stated that densely compacted GMZ bentonite has a robust interfacial self-healing capacity in terms of shear resistance.These findings contribute to the design of the bentonite buffer and facilitate the evaluation of its safe operation at specified disposal ages.

Effect of drying cracks on swelling and self-healing of bentonite-sand blocks used as engineered barriers for radioactive waste disposal

Experiments were conducted to evaluate the healing of drying cracks in air-dried bentonite-sand blocks after hydration and swelling in groundwater,providing justifications to simplify the protection of blocks prior to installation in a high-level radioactive waste repository.Synthetic groundwater was prepared to represent the geochemistry of Beishan groundwater,and was used to hydrate the blocks during the swelling pressure and swelling strain measurements,as Beishan is the most promising site for China's repository.Healing of the surface cracks was recorded by photography,and healing of the internal cracks was visualized by CT images and hydraulic conductivity of air-dried blocks.The results indicate that the maximum swelling pressure and swelling strain are primarily affected by the geochemistry of Beishan groundwater,but not affected by the drying cracks.The maximum swelling pressure and swelling strain of air-dried blocks are comparable to or even higher than the pressure and strain of fresh blocks.The maximum swelling pressure measured in strong(i.e.high ion strength)Beishan groundwater was 44%of the pressure measured in deionized(DI)water,and the maximum swelling strain was reduced to 23%of the strain measured in DI water.Nevertheless,the remained swelling of the blocks hydrated in strong Beishan groundwater was sufficient to heal the surface and internal drying cracks,as demonstrated by the pictures of surface cracks and CT images.The hydraulic conductivity of the air-dried block permeated with strong groundwater was comparable(3.7×higher)to the hydraulic conductivity of the fresh block,indicating the self-healing of drying cracks after hydration and swelling in groundwater.A simplified method of protecting the block with plastic wraps before installation is recommended,since the remained swelling of the block hydrated in Beishan groundwater is sufficient to heal the drying cracks.

Fluorographene with Narrow Lateral Size and Thickness Distributions Prepared for Enhancing Lubrication Performance of Bentonite Grease

Fluorographene(FG)with narrow lateral size and thickness distributions was prepared by a liquid-phase exfoliation method,based on liquid cascade centrifugation.The Rtec MFT-5000 tribo-meter was used to investigate the lubricating performance of bentonite grease enhanced by the as-prepared FG.The results showed that the coefficient of friction and the wear volume of bentonite grease with 0.3 wt%FG were decreased by 20.4%and 44.9%,respectively,as compared to those of the base grease.The main reason is that FG can promote the formation of the tribo-chemical reaction film consisting of complex carbon oxide,Fe_(2)O_(3)and FeF_(3)on the friction surface,which can remarkably improve the performance of friction reduction and prevent the appearance of severe wear.

Anisotropic swelling pressures of compacted GMZ bentonite infiltrated with salt solutions

In the high-level radioactive waste(HLW)deep geological repository,bentonite is compacted uniaxially,and then arranged vertically in engineered barriers.The assembly scheme induces the initial anisotropy,and with hydration,it develops more evidently under chemical conditions.To investigate the anisotropic swelling of compacted Gaomiaozi(GMZ)bentonite and the further response to saline effects,a series of constant-volume swelling pressure tests were performed.Results showed that dry density enhanced the bentonite swelling and raised the final anisotropy,whereas saline inhibited the bentonite swelling but still promoted the final anisotropy.The final anisotropy coefficient(ratio of radial to axial pressure)obeyed the Boltzmann sigmoid attenuation function,decreasing with concentration and dry density,converging to a minimum value of 0.76.The staged evolution of anisotropy coefficient was discovered,that saline inhibited the rise of the anisotropy coefficient(Dd)in the isotropic process greater than the valley(d1)in the anisotropic process,leading to the final anisotropy increasing.The isotropic stage amplified the impact of soil structure rearrangement on the macro-swelling pressure values.Thus,a new method for predicting swelling pressures of compacted bentonite was proposed,by expanding the equations of Gouy-Chapman theory with a dissipative wedge term.An evolutionary function was constructed,revealing the correlation between the occurrence time and the pressure value due to the structure rearrangement and the former crystalline swelling.Accordingly,a design reference for dry density was given,based on the chemical conditions around the pre-site in Beishan,China.The anisotropy promoted by saline would cause a greater drop of radial pressure,making the previous threshold on axial swelling fail.

Effect of shaking time, ionic strength, temperature and pH value on desorption of Cr(III) adsorbed onto GMZ bentonite

The Cr（III） desorption experiments of Gaomiaozi （GMZ） bentonite in aqueous solutions were performed. The variables affecting the desorption behaviors, such as contact time, concentration of the desorbent, pH value of the solution, temperature and desorption isotherms, were investigated by the batch experiments. The results show that the adsorbed Cr（III） on GMZ bentonite can be easily extracted by the desorbent. Kinetics examination shows that desorption is slower than adsorption, and the desorption rate increases with time and reaches the equilibrium after 3 h. The final desorption ratios of Cr（III） are 89.4%, 56.5%and 77.2%in the desorption solution with 0.1 mol/L HCl, 1 mol/L NaCl, and 1 mol/L CaCl2, respectively, and the concentration can promote the desorption progress. Furthermore, the results of successive regeneration cycles indicate that the bentonite has a good regeneration ability and reusability. The pH value is an important factor in the Cr（III） desorption from the GMZ bentonite. The results of adsorption and desorption isotherms show that both adsorption and desorption isotherms are consistent with the Freundlich equation. The comparison of adsorption and desorption isotherms implies that the adsorption/desorption hysteresis is negligible and the transport of Cr（III） in bentonite can be described by a reversible adsorption process.

Synthesis of nano-MoS_2/bentonite composite and its application for removal of organic dye

A nano-MoS2/bentonite composite was synthesized by calcinating MoS3 deposited on bentonite in H2. The obtained composite was characterized using thermogravimetric analysis, X-ray diffractometer, scanning electron microscope and transmission electron microscope. The results show that nano-MoS2 particles are distributed on the surface of bentonite and form layered structures with layer distance of about 0.64 nm. The composite presents an excellent performance for the removal of methyl orange. Some operation conditions affect the removal efficiency of methyl orange, such as dosage of composite, initial concentration of methyl orange, temperature and pH value. However, light source does not influence the removal efficiency. The removal mechanism is attributed to the adsorption of methyl orange on the nano-MoS2/bentonite composite. The adsorption of methyl orange on the composite is in accordance with the pseudo-second-order kinetic model.

Effect of water chemistry on the hydro-mechanical behaviour of compacted mixtures of claystone and Na/Ca-bentonites for deep geological repositories

In the French deep geological disposal for radioactive wastes,compacted bentonite/claystone mixtures have been considered as possible sealing materials.After emplacement in place,such mixtures are hydrated by the site solution as well as the cement solution produced by the degradation of concrete.In this study,the effects of synthetic site solution and cement solution on the hydro-mechanical behaviour of compacted mixtures of claystone and two types of bentonites(MX80 Na-bentonite and Sardinia Cabentonite)were investigated by carrying out a series of swelling pressure,hydraulic conductivity and mercury intrusion porosimetry(MIP)tests.It was found that for the MX80 bentonite/claystone mixture hydrated with synthetic site solution,the swelling capacity was reduced compared to the case with deionised water owing to the transformation of Na-montmorillonite to multi-cation dominant montmorillonite by cation exchanges.For the Sardinia bentonite/claystone mixture,the similar increasing rate of swelling pressure was observed during the crystalline swelling process for different solutions,suggesting insignificant cation exchanges.Additionally,the cations in the synthetic site solution could reduce the thickness of diffuse double layer and the osmotic swelling for both MX80 bentonite/claystone and Sardinia bentonite/claystone mixtures.The large-pore volume increased consequently and enhanced water flow.In the cement solution,the hydroxide could also dissolve the montmorillonite,reducing the swelling pressure,and increase the large-pore volume,facilitating the water flow.Furthermore,the decrease of swelling pressure and the increase of hydraulic conductivity were more significant in the case of low dry density because of more intensive interaction between montmorillonite and hydroxide due to the high permeability.

Characterization, Acid Activation and Bleaching Performance of Bentonite from Xinjiang

Bentonite produced in Xiazijie, Xinjiang (China) was characterized by X-ray diffraction (XRD), dif- ferential thermal analysis (DTA), thermogravimetric analysis (TG) and cation exchange capacity (CEC). The ben- tonite is composed of dioctahedral montmorillonite with predominant quantity, certain amounts of quartz, feldspar and illite and minor amounts of kaolinite, gypsum, etc. The raw bentonite has a CEC of 0.6497 meq·g-1 and allows to be characterized as typical sodium bentonite. In order to bleach cottonseed oil, optimum conditions for sulfuric acid activation of the raw bentonites were investigated, which were obtained by selecting various acid strength, at 96—98℃ and activating for 4h with 1︰2 solid-liquid ratio. The acid activation bentonites were suitable for decol- orization of cottonseed oil through removing carotene and chlorophyll. The bleaching capabilities of different pig- ments with activated bentonite with treatment of 25% sulfuric acid were 70.3%, 73.1%, 83.2%, 81.8% and 88.9%, respectively. Bleaching with acid activated bentonite gave oils lower peroxide values and acid values.

Effect of temperature on soil-water characteristics and hysteresis of compacted Gaomiaozi bentonite

Laboratory tests under different constraint conditions were carried out to obtain the soil-water retention curves(SWRCs) of highly-compacted confined/unconfined Gaomiaozi(GMZ) bentonite at 20,40 and 80 ℃,respectively. The effect of temperature on the soil-water characteristics of the highly-compacted GMZ bentonite was analyzed. The results show that the water retention capacity of the highly-compacted GMZ bentonite decreases as the temperature increases under unconfined and confined conditions. At a certain temperature,the constraint conditions have little influence on the water retention capacity of the compacted bentonite at high suction,but the water retention capacity of the confined specimen is lower than that of the unconfined specimen at low suction. Under unconfined conditions,the hysteretic behaviour of the compacted bentonite decreases with increasing temperature. At high suction(>4 MPa) ,the hysteretic behaviour of the unconfined bentonite tends to increase with the decrease of the suction. In summary,the hysteretic behaviour of the compacted bentonite is not significant.

Experimental investigation into temperature effect on hydro-mechanical behaviours of bentonite

The bentonite barrier of underground repositories for high-level radioactive waste will be hydrated by the groundwater while it is subjected to high temperatures due to the radioactive decay of the wastes. These changes of temperature affect the hydraulic and mechanical responses of bentonite, which has important effects on design and performance of repositories. The temperature influence on the hydro-mechanical behaviour of bentonite was studied in this paper by experiments, which were carried out with the Spanish FEBEX bentonite compacted at dry densities expected in the＇ repository （from 1.5 to 1.8 Mg/m^3）. The dependence of the swelling strains of bentonite on the temperature has been measured from 30℃ to 90 ℃. At high temperatures the swelling capacity of clay slightly decreases. Also, a clear decrease of swelling pressure as a function of temperature was observed for the same dry densities. Nevertheless, the deformation of bentonite is more dependent on the stress than the temperature. An increase in the permeability of water saturated bentonite with temperature has also been detected. The water retention curves of bentonite compacted at different dry densities were determined under isochoric conditions and in the range of temperatures from 20 ℃ to 120℃. For a given density and water content, the suction decreases as the temperature increases at a rate, which is larger than the one predicted on the basis of water surface tension changing with temperature. Mechanisms related to the physico-chemical interactions that take place at microscopic level, in particular the transfer of interlayer water to the macropores triggered by temperature, seem to explain qualitatively the experimental observations.

Statistical design and kinetic and thermodynamic studies of Ni(Ⅱ) adsorption on bentonite

The adsorption of the bentonite toward Ni(II) from aqueous solution was studied to obtain optimum conditions,equilibrium model,thermodynamic and kinetic parameters.Statistical method was used to evaluate maximum amount of adsorbed Ni(II).In this work,p H of solution during stirring,contact time,initial Ni(II) concentration,particle size of bentonite and amount of bentonite were considered as effective parameters which should be examined.The increase of temperature has negative effect on the Ni(II) adsorption.The equilibrium data were correlated well with Freundlich and Dubinin–Radushkevich isotherm models the correlation coefficients of which are(R^2) 0.994 and 0.971,respectively.This model indicates heterogeneous and chemical absorption or ion exchange process.The values of thermodynamic parameters such as ΔH°,ΔS° and ΔG° of nickel adsorption reveal that it is a spontaneous,exothermic and associative process.The experimental data fit the pseudo-second-order kinetic very well with correlation coefficient(R^2) more than 0.995.

Adsorption Kinetics of β-Carotene and Chlorophyll onto Acid-activated Bentonite in Model Oil

The textural properties of acid-activated bentonite （AAB）, which were prepared using four different concentrations of sulfuric acid, were analyzed by adsorption-desorption isotherm of nitrogen using an automated specific surface area and porosity analyzer. The total pore volume, specific surface area and average pore diameter of these four kinds of AAB show a regular changing trend, increasing first and then decreasing, the optimum of which can be achieved at a sulfuric acid concentration of 25% （sample A25）. The kinetic analysis of the adsorption of β-carotene and chlorophyll in model oil solutions, namely, xylene and edible oil solution, has been investigated by using AAB. Experimental results indicated that the adsorption data fit the pseudo-second-order model well. The whole adsorption process of the two pigments on AAB was divided basically into two parts： the initial adsorption of pigments was rapid in the first l0 rain, followed by a slower adsorption process till equilibrium was attained at 60 rain. In addition, the amount and rate of adsorption on A25 increase synchronously with the initial pigment concentration and temperature. The results showed that the adsorption kinetics behavior of AAB with respect to the pigments is not influence by the xylene and edible oil solution.

Properties of Bentonite Enhanced Loess and Laterite

Loess and laterite distributed widely in the northern and southern China cannot be directly used as the natural barrier to isolate the solid waste because of their high hydraulic conductivity. In this paper, they are enhanced by bentonite to improve their hydraulic performance. The impact of bentonite content and water content on compressive strength of the compacted soil was investigated. The effects of bentonite content, water content, dry density and hydraulic gradient on the hydraulic conductivity were studied in detail. For the laterite and the laterite with 8% of bentonite, the experimental results of hydraulic conductivity can be applied in the engineering design. However, for the loess and the bentonite enhanced loess, those of hydraulic conductivity can not be directly applied in the engineering design because their hydraulic performance does not comply with the Darcy's law. These experimental results have to be carefully modified before application.

Engineering behavior and sedimentation behavior of lead contaminated soil-bentonite vertical cutoff wall backfills

Soil-bentonite （SB） vertical slurry cutoff wall is a useful treatment for urban industrial contaminated sites. Due to the clay-heavy metal interaction, significant changes would occur in the engineering behavior of SB cutoff walls. However, previous study is limited to kaolinitic soils or montmorillonitic soils along using solidum chloride and/or calcium chloride as target contaminant. In this work, a series of oedometer tests were conducted to investigate the effects of lead （Pb） on the compressibility and the permeability of kaolin-bentonite （KB） mixtures, a simplified model of in-situ SB cutoff wall backfills. In addition, sedimentation tests were conducted to interpret the mechanism controlling the change of compressibility and permeability from the perspective of soil fabric. The Pb-contaminated KB mixtures for oedometer tests and sedimentation tests were prepared with bentonite contents of 0, 5%, 10%, and 15% by dry mass, and they were mixed with pre-determined volume of lead nitrate solution based on designed Pb concentration and solid-to-solution ratio. The Pb concentration was controlled as 0, 0.1, 0.5, 1.0, 5.0, 10, and 50 mg/g with a solid-to-solution ratio of approximate 0.5. The prepared KB mixtures with bentonite contents of 0, 5%, and 10% were chosen for the sedimentation tests. They were freeze-dried and mixed with DDI with a solid-to-solution ratio of 10 g/100 mL. The results indicate that pH, compressibility, and permeability of KB mixture changed considerably with respect to Pb concentration. It is concluded that the fabric of KB mixture, depending on the particle-particle interaction subjected to different ranges of pH and Pb concentration, governs the sedimentation behavior and permeability. The results of liquid limit （WE） cannot be explained in terms of the sedimentation behavior since it is only ionic-dependent.

Determination of full-scale pore size distribution of Gaomiaozi bentonite and its permeability prediction

Gaomiaozi(GMZ)bentonite is a potential buffer/backfill material for a deep geological disposal of highlevel radioactive waste.It has a wide pore size distribution(PSD)with sizes ranging from several nanometers to more than one hundred microns.Thus,properly characterizing the pore structures of GMZ bentonite is a challenging issue.In this study,pressure-controlled porosimetry(PCP),ratecontrolled porosimetry(RCP),and scanning electron microscopy(SEM)were used to investigate the PSD of GMZ bentonite,The results indicate that each method has its limitation,and a combined use of PCP and RCP is suitable to obtain the full-scale PSD of GMZ bentonite.Moreover,we also compared the full-scale PSD with nuclear magnetic resonance(NMR)result.It is found that there is no significant difference in the range of PSD characterization between NMR and mercury intrusion method(PCP and RCP).However,in a ce rtain range,the detection accuracy of NMR is higher than that of mercury injection method.Finally,permeability prediction based on PCP and SEM data was conducted,and both of the two methods were found to be able to predict the permeability.The combined method is effective to obtain the full-scale PSD of GMZ bentonite,which is the key to estimation of the sealing ability of bentonite buffer.

Influence of temperature on swelling deformation characteristic of compacted GMZ bentonite-sand mixtures

Laboratory swelling deformation tests were carried out on compacted GMZ bentonite and bentonite-sand mixtures with 30%and 50%sand contents at 20,40,60,80 and 90°C with infiltration of distilled water.Influence of temperature,initial dry density,and quartz sand content on the swelling deformation characteristic of compacted bentonite specimens was analyzed.Results indicate that the swelling deformation process is accelerated,and the maximum swelling strain increases with the increase in temperature,while the maximum swelling strain tends to be stable with increasing temperature.In the meantime,the temperature effects depend on both of the sand content and the initial dry density of the specimens,the increases of the maximum swelling strain induced by increasing temperature,are enlarged by increasing sand content or initial dry density.Adding of quartz sand to bentonite not only influences the integrality of bentonite specimen,but also increase the microfissuring in area on quartz sand,which are advantageous to the heat transfer,leading to the increase of swelling deformation capacity of the specimen.The increased dry density relatively increases the bentonite content,so the swelling property is enhanced.However,no change on mineral composition of bentonite was observed when temperature was changed from 20 to 90°C.

Sorption of wastewater containing reactive red X-3B on inorgano-organo pillared bentonite

Bentonite is a kind of natural clay with good exchanging ability. By exchanging its interlamellar cations with various soluble cations, such as quaternary ammonium cations and inorganic metal ions, the properties of natural bentonite can be greatly improved. In this study, hexadecyltrimethylammonium bromide (HDTMA), CaCl2, MgCl2, FeCl3, AlCl3 were used as organic and inorganic pillared materials respectively to produce several kinds of Ca-, Mg-, Fe-, Al-organo pillared bentonites. Sorption of reactive red X-3B on them was studied to determine their potential application as sorbents in wastewater treatment. The results showed that these pillared bentonites had much improved sorption properties, and that the dye solutions’ pH value had some effect on the performance of these inorgano-organo pillared bentonites. Isotherms of reactive X-3B on these pillared bentonites sug-gested a Langmuir-type sorption mechanism.

Effect of background electrolytes on the adsorption of nitroaromatic compounds onto bentonite

To further elucidate interaction of nitroaromatic compounds with mineral surface, the sorption of m-dinitrobenzene （m-DNB） and nitrobenzene to original bentonite in aqueous solution containing different electrolytes （i.e., KCl, NH4Cl, CaCl2 and Tetramethylammonium bromide （TMAB）） was studied. The sorption of m-DNB was greatly enhanced with the presence of KCl and NH4Cl, while little influence was observed with CaCl2 and TMAB, following the order of KCl 〉 NH4Cl 〉〉 TMAB, CaCl2, or DI water. For nitrobenzene, sorption enhancement only occurred at high nitrobenzene concentrations in the presence of KCl, and the solute equilibrium concentration at inflexion point was lowered with increasing KCl concentration. These sorption enhancements were significantly promoted with the increase of electrolyte concentration. The salting-out effect is insufficient to account for the sorption enhancement by original bentonite with increasing KCI or NH4Cl concentration. X-ray diffraction patterns of bentonite suspensions indicated that the sorption enhancement of m-DNB was attributed to the intercalation of K^＋ or NH4^＋ into bentonite interlayer and then dehydration with m-DNB to form inner-sphere complexes, which caused previously expanded bentonite interlayers to collapse in aqueous suspension, thus further enhanced the interaction of phenyl with siloxane surface. In comparison, the sorption enhancement of NB is attributed to the formation of outer-sphere complexes with K^＋ at high solute-loadings （〉 20（0-400 mg/kg）. The sorption of m-DNB to initially modified TMA^＋-bentonite and K^＋-bentonite was almost the same as respective sorption to original bentonite in solution containing TMA^＋ and K^＋.