Anion exclusion effects in compacted bentonites: Towards a better understanding of anion diffusion

Diffusion of ³⁶Cl⁻ in compacted bentonite was studied using through-diffusion, out-diffusion and profile analysis techniques. Both the bulk dry density of the bentonite and the composition of the external solution were varied. Increasing the bulk dry density of the bentonite resulted in a decrease of both the effective diffusion coefficient and the Cl-accessible porosity. Increasing the ionic strength of the external solutions resulted in an increase of both the effective diffusion coefficient and the Cl-accessible porosity. This can be explained by anion exclusion effects (Donnan exclusion). At high ionic strength values (I ? 1 M NaCl) the Cl-accessible porosity approaches the interparticle porosity. This interparticle porosity is the difference between the total and interlayer porosity of the bentonite. The interlayer porosity was found to depend on the degree of compaction. Up to a bulk dry density of 1300 kg m⁻³ the interlayer is built up of 3 water layers. Between 1300 and 1800 kg m⁻³ the interlayer water is reduced from 3 to 2 layers of water. Above 1800 kg m⁻³ evidence for a further decrease to 1 layer of water was found. These findings are in agreement with X-ray data found in the literature showing a decrease of the basal spacing of montmorillonite (the main clay mineral in bentonite) with increasing degree of compaction. The relationship between the effective diffusion coefficient of Cl⁻ and the diffusion-accessible porosity can be described by an empirical relationship analogous to Archie’s law. To predict the effective diffusion coefficient of Cl⁻ in compacted bentonite, the diffusion coefficient of Cl⁻ in water, the bulk dry density and the ionic strength of the pore water have to be known.     

Porewater chemistry in compacted bentonite: Application to the engineered buffer barrier at the Olkiluoto site

Compacted bentonite is used as sealing and buffer material in engineered barrier systems (EBS) of high-level radioactive waste repositories. The chemical characteristics of this clay and its porewater affect the migration of radionuclides eventually released from the waste. They also determine the integrity and long-term performance of the clay barriers. Key features are the structural negative charge and the large proportion of structural (interlayer) water of the main mineral montmorillonite, which leads to exclusion of anions and a surplus of cations in a large part of the porosity space. The objective of this contribution was to assess the impact of different porosity model concepts on porewater chemistry in compacted bentonite in the context of the planned Finnish spent nuclear fuel repository at Olkiluoto. First, a structural model based on well-established crystallographic and electrostatic considerations was set up to estimate the fractions of the different porosity types. In view of the uncertainty related to the chemical properties of the interlayer water, two very different model concepts (anion-free interlayer, Donnan space), together with a well-established thermodynamic model for bentonite, were applied to derive the porewater composition of the bentonite buffer at Olkiluoto. The simulations indicate very similar results in the “free” water composition for the two models and thus support the validity of the reference porewater concept commonly used in performance assessment of waste repositories. Differences between the models are evident in the composition of the water affected by the surface charge (i.e. diffuse double layer and interlayer). These reflect the conceptual uncertainty in current multi-porosity diffusion models.     

An upscaling method and a numerical analysis of swelling/shrinking processes in a compacted bentonite/sand mixture

This paper presents an upscaling concept of swelling/shrinking processes of a compacted bentonite/sand mixture, which also applies to swelling of porous media in general. A constitutive approach for highly compacted bentonite/sand mixture is developed accordingly. The concept is based on the diffuse double layer theory and connects microstructural properties of the bentonite as well as chemical properties of the pore fluid with swelling potential. Main factors influencing the swelling potential of bentonite, i.e. variation of water content, dry density, chemical composition of pore fluid, as well as the microstructures and the amount of swelling minerals are taken into account. According to the proposed model, porosity is divided into interparticle and interlayer porosity. Swelling is the potential of interlayer porosity increase, which reveals itself as volume change in the case of free expansion, or turns to be swelling pressure in the case of constrained swelling. The constitutive equations for swelling/shrinking are implemented in the software GeoSys/RockFlow as a new chemo‐hydro‐mechanical model, which is able to simulate isothermal multiphase flow in bentonite. Details of the mathematical and numerical multiphase flow formulations, as well as the code implementation are described. The proposed model is verified using experimental data of tests on a highly compacted bentonite/sand mixture. Comparison of the 1D modelling results with the experimental data evidences the capability of the proposed model to satisfactorily predict free swelling of the material under investigation. Copyright © 2004 John Wiley & Sons, Ltd.     

碱−热环境下MX80膨润土导热性能试验研究

以美国怀俄明州钠基（MX80）膨润土为研究对象,采用热探针法测定碱−热环境下MX80膨润土的导热系数,探讨了温度、碱液强度和干密度对试样导热系数λ的影响规律,并选择部分试样进行了X射线衍射（X-ray diffraction,简称XRD）和扫描电镜（scanning electron microscope,简称SEM）试验,揭示了碱−热环境下MX80膨润土导热性能演变的微观机制。试验结果表明：MX80膨润土的导热系数λ随碱液含量和干密度的递增而增大;在不同碱液含量条件下,膨润土的导热系数均随温度升高而增大,且碱液含量越高,导热系数的温度效应越显著;干密度较小时,膨润土导热系数λ随温度升高而增大的影响越明显,主要原因是温度促进了试样内部的水汽潜热传输;同一温度和干密度条件下,热传导系数λ随着碱液pH值的升高而降低6,且pH值越高,则λ降幅越明显,主要原因是强碱溶液腐蚀了膨润土的蒙脱石成分,减少了试样内石英含量,增大了膨润土试样的孔隙率,进而降低了膨润土导热系数,这与测试试样的XRD和SEM结果相吻合。     

Characteristics,modification and environmental application of Yemen’s natural bentonite

The bentonite deposit of Lahij Province, Yemen, has very promising commercial applications due to its mineralogy and physical and chemical properties. It was examined to determine its mineralogical composition, chemical and physical properties of the bentonite deposit, purity and sodium-exchanged bentonite. Modified bentonite was synthesized by exchanging cetyltrimethylammonium cations for inorganic ions on the bentonite and its adsorption properties for ammonium were characterized in batch experiments. Analytical methods were carried out to study the bentonite comprising X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy, chemical analysis and kinetic and isotherm models were also tested. The results have shown that the purification of bentonite resulted in a bentonite fractions of the total sample composed of montmorillonite and <5 % quartz. The XRD data showed that the interlayer spacing (d ₀₀₁) of bentonite decreased from 15.3 to 12.5 Å and then increased to 19.7 Å. Moreover, high cation exchange capacity, good water absorption and high swelling capacity were also obtained. The results have shown that the modified bentonite was more effective than the natural bentonite for ammonium removal. In addition to that, pseudo-second-order kinetic model, Freundlich and the Langmuir models described the adsorption kinetics and isotherm well. It was concluded that Yemen (Alaslef) bentonite can be potential adsorbents for ammonium removal.     

Effects of dry density and exchangeable cations on the diffusion process of sodium ions in compacted montmorillonite

As a part of the safety assessment of the geological disposal of high-level radioactive waste, the effects of dry density and exchangeable cations on the diffusion process of Na⁺ ions in compacted bentonite were studied from the viewpoint of the activation energy for diffusion. The apparent self-diffusion coefficients of Na⁺ ions in compacted Na-montmorillonite and in a Na- and Ca-montmorillonite mixture were determined by one-dimensional, non-steady diffusion experiments at different temperatures and dry densities. A unique change in activation energy as a function of dry density was found for the Na⁺ ions in compacted Na-montmorillonite. The activation energy suddenly decreased from 18.1 to 14.1 kJ mol^− 1 as the dry density increased from 0.9 to 1.0 Mg m^− 3, whereas it increased to 24.7 kJ mol^− 1 as the dry density increased to 1.8 Mg m^− 3. Examination of the effect of exchangeable cations on the activation energies determined that the activation energies were almost constant, approximately 25 kJ mol^− 1, for the montmorillonite specimens at a dry density of 1.8 Mg m^− 3. However, three different activation energy values were obtained at a dry density of 1.0 Mg m^− 3. These findings cannot be explained by the conventional diffusion model (the pore water diffusion model), which suggests that the predominant diffusion process alternates among pore water diffusion, interlayer diffusion, and external surface diffusion.     

Modelling the interaction of bentonite with hyperalkaline fluids

Many designs for geological disposal facilities for radioactive and toxic wastes envisage the use of cement together with bentonite clay as engineered barriers. However, there are concerns that the mineralogical composition of the bentonite will not be stable under the hyperalkaline pore fluid conditions (pH > 12) typical of cement and its properties will degrade over long time periods. The possible extent of reaction between bentonite and cement pore fluids was simulated using the reaction-transport model, PRECIP. Key minerals in the bentonite (Na-montmorillonite, analcite, chalcedony, quartz, calcite) were allowed to dissolve and precipitate using kinetic (time-dependent) reaction mechanisms. Simulations were carried out with different model variants investigating the effects of: temperature (25 and 70 °C); cement pore fluid composition; dissolution mechanism of montmorillonite; rates of growth of product minerals; solubilities of product minerals; and aqueous speciation of Si at high pH. Simulations were run for a maximum of 3.2 ka. The results of all simulations showed complex fronts of mineral dissolution and growth, driven by the relative rates of these processes for different minerals. Calcium silicate hydrate (CSH) minerals formed closest to the cement-bentonite boundary, whereas zeolites and sheet silicates formed further away. Some growth of primary bentonite minerals (analcite, chalcedony, calcite and montmorillonite) was observed under certain conditions. Most alteration was associated with the fluid of highest pH, which showed total removal of primary bentonite minerals up to 60 cm from the contact with cement after ∼1 ka. The maximum porosity increase observed was up to 80–90% over a narrow zone 1–2 cm wide, close to the cement pore fluid- bentonite contact. All simulations (except that with alternative aqueous speciation data for Si) showed total filling of porosity a few cms beyond this interface with the cement, which occurred after a maximum of 3.2 ka. Porosity occlusion was principally a function of the growth of CSH minerals such as tobermorite. There was very little difference in the alteration attained using different model variants, suggesting that bentonite alteration was not sensitive to the changes in parameters under the conditions studied, so that transport of pore fluid through the bentonite governed the amount of alteration predicted. Principal remaining uncertainties associated with the modelling relate to assumptions concerning the evolution of surface areas of minerals with time, and the synergy between changing porosity and fluid flow/diffusion.     

高庙子膨润土中蒙脱石碱性溶蚀的矿物学证据

高放废物地下处置库运营过程中,衬砌混凝土在地下水作用下产生的强碱性溶液,会扩散进入膨润土缓冲屏障,长期将使屏障性能发生退化。采用不同 pH 值的 KOH 溶液模拟衬砌混凝土溶出的碱性溶液,在室内进行为期一年的常温接触扩散试验,开展X射线荧光光谱（X-ray fluorescence spectroscopy,简称XRF）、X射线衍射（X-ray diffraction,简称 XRD）、扫描电镜（scanning electron microscope,简称 SEM）和能谱（energy dispersive spectrometry,简称 EDS）试验,研究强碱性溶液缓慢扩散对高庙子膨润土矿物的影响。XRF试验结果表明,当 KOH 溶液的 pH>12.6时,膨润土中 Si 元素的含量开始减少,即含Si 矿物蒙脱石、石英、方石英等发生了溶解;同时,K元素含量增多,表明膨润土与碱溶液发生离子交换反应,溶液中大量的K⁺进入蒙脱石层间。XRD 试验结果表明,在 pH=12.6时,蒙脱石矿物的 001峰开始右移、变宽,峰值强度大大减弱;在pH>13时,衍射角θ整体向右偏,晶面间距由原始膨润土样的1.385 3 nm（13.853 Å）减小为1.221 0 nm（12.210 Å）,表明蒙脱石矿物晶层被压缩。随着 KOH 溶液 pH 值增大,膨润土中蒙脱石、石英等矿物的含量明显减少,长石类矿物的含量逐渐增加,伊利石和斜发沸石的含量也呈现略微增多的趋势。SEM 试验结果表明,随着溶液 pH 的增大,蒙脱石部分晶层会发生重叠,进而产生部分裂隙和孔洞,加速蒙脱石的溶蚀进程。在为期一年的接触扩散试验中,pH=13.8的 KOH 溶液扩散深度超过7.5 mm,并且在碱溶液与膨润土接触面上观察到新生成的伊利石微晶,证实强碱性溶液会导致蒙脱石溶解及伊利石化。     

蒙脱石对赖氨酸和壳聚糖的吸附实验研究

粘土矿物对有机质的吸附是自然界重要的过程之一。科学界对于有机质与粘土矿物的相互作用过程和机制研究仍处 于一个比较薄弱的阶段。该文采用天然有机质赖氨酸（左旋） 和壳聚糖与蒙脱石进行室内合成模拟实验,通过X射线衍 射、化学分析和红外光谱分析的手段对反应产物进行系统研究。结果表明,蒙脱石对赖氨酸和壳聚糖的吸附均存在两种机 制：阳离子交换和有机分子间的相互吸引。赖氨酸在蒙脱石层间的排布有三种构型,随着赖氨酸浓度的增加分别以倾斜 式、垂直呈“之”字形排列,最后形成第二排并可能生成简单肽;氨基酸的净电荷是影响吸附过程的重要因素,主要与pH 值相关。壳聚糖能在蒙脱石层间形成分层结构,溶液的pH值和无机盐的存在都会影响吸附过程。壳聚糖-蒙脱石复合体在 常温常压下水溶液中能稳定存在,而相同条件下赖氨酸易从蒙脱石层间释放,这主要是由有机质本身的性质以及有机质和 蒙脱石的结合方式决定的。     

Comparative study of tracer diffusion of HTO, Na and Cl in compacted kaolinite, illite and montmorillonite

The through-diffusion of HTO, ²²Na⁺ and ³⁶Cl⁻ in kaolinite, homo-ionic Na-illite and homo-ionic Na-montmorillonite was measured at a high degree of compaction as a function of the salt concentration in the ‘external solution’, i.e. in the solution in contact with the clay sample. The clays were chosen for this study because of their differences in the number and nature of ion exchange sites leading to different proportions of interlayer-, inter-particle and free pore water. It was found that the diffusive mass transfer of Na⁺ in Na-montmorillonite and Na-illite increased with decreasing external salt concentration, while the opposite trend was observed for the diffusion of Cl⁻. These trends are more pronounced in the case of Na-montmorillonite than in Na-illite, while almost no salt effect was observed for kaolinite. Similarly no salt effect was observed for the diffusion of HTO through all of the clays tested. These observations are in agreement with a conceptual model where it is assumed that cations diffuse preferentially in the interlayer or diffuse double-layer porosity, while anions are almost completely excluded from these regions. In the case of Na⁺ diffusion, the salt effects can be explained by an influence on the concentration gradient of diffusing cations, while in the case of Cl⁻ the external salt concentration has an effect on the accessible porosity. Effective diffusion coefficients of Cl⁻ fulfil the same relationship to porosity as those of the uncharged HTO, when using accessible porosities for such a comparison. Furthermore it is shown that pore diffusion coefficients for the three tracers are fairly well correlated with the respective diffusion coefficients in bulk water, if the effective diffusion coefficients for Na⁺ are derived from calculated tracer concentration gradients in the interlayer or diffuse double-layer porosities.     

Design of bentonite/crushed rock seals

Summary The use of bentonite/crushed rock mixtures to form hydraulic barriers has greatly increased in recent years. To obtain an appropriate composition for such mixture sealants generally requires extensive laboratory work. Bentonite content and gradation of the crushed rock component are two key parameters in the seal design. This study investigates the effect of crushed rock gradation on the bulk porosity and permeability of systems of crushed tuff particles. Five different gradations are selected from the literature. The bulk porosity of systems of crushed tuff in the presence of bentonite is examined. The Fuller-Thompson gradations yield denser particle arrangements. For mixture samples containing 15% bentonite by weight, the amount of clay accounts for only 45 to 56% of the weight required to fill the interparticle pore space. The bentonite occupancy percentage amounts to 65 to 80% and 75 to 86.5% for samples having 25 and 35% bentonite by weight, respectively. The water content of bentonite at saturation is reduced and the resistance to piping and flow of bentonite is enhanced by the addition of clay. To reduce the bulk porosities of the mixtures containing 25% or more bentonite, a compaction energy higher than the standard Proctor compaction is necessary.     

Multicomponent diffusion of a suite of tracers (HTO, Cl, Br, I, Na, Sr, Cs) in a single sample of Opalinus Clay

Diffusion experiments with HTO, ³⁶Cl⁻, Br⁻, I⁻, ²²Na⁺, ⁸⁵Sr²⁺ and ¹³⁴Cs⁺ at trace concentrations in a single sample of Opalinus Clay are modeled with PHREEQC’s multicomponent diffusion module. The model is used first in a classical approach to derive accessible porosities, geometrical factors (the ratio of pore tortuosity and constrictivity) and sorption behavior of the individual tracers assuming that the clay is homogeneous. The accessible porosity for neutral species and cations is obtained from HTO, the anion exclusion volume from ³⁶Cl⁻ and Br⁻, and the cation exchange capacity from ²²Na⁺. The homogeneous model works well for tritium, the anions and ²²Na⁺. However, the ⁸⁵Sr²⁺ and ¹³⁴Cs⁺ experiments show an early arrival of the tracer and a front-form that suggest a dual porosity structure. A model with 10% dead-end pores, containing 19% of the total exchange capacity, can satisfactorily calculate all the experimental data. The Cs⁺ diffusion model builds on a 3-site exchange model, constructed from batch sorption data. The excellent agreement of modeled and measured data contradicts earlier reports that the exchange capacity for Cs⁺ would be smaller in diffusion than in batch experiments.The geometrical factors for the anions are 1.5 times larger than for HTO, and for the cations 2-4 times smaller than for HTO. The different behavior is explained by a tripartite division of the porespace in free porewater, diffuse double layer (DDL) water, and interlayer water in montmorillonite. Differences between estimated and observed geometrical factors for cations are attributed to increased ion-pairing of the divalent cations in DDL water as a result of the low relative dielectric permittivity. Interlayer and/or surface diffusion contributes significantly to the diffusive flux of Cs⁺ but is negligible for the other solutes. The geometrical factors for anions are higher than estimated, because pore constrictions with overlapping double layers force the anions to take longer routes than HTO and the cations. Small differences among the anions can also be attributed to different ion-pairing in DDL water.     

我国高放废物处置库缓冲／回填材料压实膨胀特性研究

本文研究了我国高放废物地质处置库缓冲／回填材料－内蒙古高庙子膨润土的压实、膨胀力和膨胀变形特性。实验结果表明，膨润土样品的压实密度与压制压力和蒙脱石含量有关，膨胀力与样品压实密度和蒙脱石含量有关，样品在荷载作用下膨胀变形明显减小。     

根据蒙脱石的层间水化状态探讨南京仙林盆地的地面沉降及其趋势

引用B rown等和F itts等提出的蒙脱石层间水化状态修正的土壤孔隙率的计算方程,以此建立蒙脱石层间脱水作用所产生的次要地面沉降量的数学表达式,对位于山间沟谷型沉积盆地的南京仙林新市区可能产生的地面沉降量进行了模拟计算。结果表明:该地区由蒙脱石层间水部分释出而产生的次要沉降量为6.85 cm,估计该地区过去曾发生34~46 cm的地面沉降;如果蒙脱石残余层间水全部释出,那么该地区可能还存在96.47 cm的地面沉降。虽然96.47 cm的地面沉降在真实的外界环境下不可能实现,但对下一步地面沉降灾害的防治具有一定的警示作用。蒙脱石层间脱水作用及其对地面沉降影响的研究,对地面沉降趋势的预测具有启示作用。     

蒙脱石层间水化状态对土壤孔隙率计算的修正及其在地面沉降中的应用

用蒙脱石层间水化状态修正了土壤孔隙率的计算方程,以此建立蒙脱石层间脱水作用所产生的次要地面沉降量的数学表达式,并对无锡石塘湾地面沉降区进行了模拟计算。无锡石塘湾地区因蒙脱石层间释水所产生的次要地面沉降量为39.02 cm,占整个沉降量的19.51%,人工回灌后,次要地面沉降量变为36.04 cm,占整个沉降量的18.02%,表明人工回灌是阻止地面继续沉降的有效措施之一。计算表明,如果蒙脱石残余层间水全部释出,那么无锡石塘湾地区可能有117.39 cm的地面沉降空间。虽然这一结果在真实的外界环境下不可能实现,但对下一步就地面沉降灾害的治理、防治具有一定的警示作用。蒙脱石层间脱水作用及其对地面沉降影响的研究,可能对地面沉降趋势的预测具有启示作用。     

Diffusion and sorption of Cs, I and HTO in samples of the argillaceous Wakkanai Formation from the Horonobe URL, Japan: Clay-based modeling approach

Diffusion and sorption behaviors of cationic Cs⁺, anionic I⁻ and neutral HTO in samples of the Wakkanai Formation from the Horonobe underground research laboratory (URL), Japan, were investigated as a function of ionic strength (I) of synthetic groundwater by through-diffusion and batch sorption experiments and mechanistic modeling. The effective diffusivities (D_e) measured by through-diffusion experiments showed cation excess and anion exclusion effects, which were strongly dependent on I; D_e for Cs⁺ decreased as I increased, D_e for I⁻ showed the opposite dependency and D_e for HTO showed no dependence. The sorption of Cs⁺ measured by through-diffusion and batch sorption experiments were described by Freundlich isotherms with consistent parameters and decreased with I as a result of competitive ion exchange.Diffusion and sorption behaviors were interpreted by assuming the clay components of illite and smectite control diffusion and sorption mechanisms. The component additive (CA) sorption model, which includes illite and smectite contents and their ion exchange constants, provided a reasonable account of the Cs⁺ sorption trends measured as functions of I and Cs concentration. The diffusion model was developed by coupling the electrical double layer (EDL) model, describing the change of ionic concentrations (cation excess and anion deficit) and viscoelectric effects caused by electrostatic interaction at negatively charged clay surfaces, and a simplified pore model assuming one type of pore shape and includes their size distribution. When averaging the electrostatic effects by using the pore surface area distribution, the model could predict the cation excess and anion exclusion effects, and its dependence on I reasonably well. This result implies the nanoscale pores dominating the pore surface area can strongly impact on ionic diffusion in argillaceous rocks. The clay-based modeling approach described here provides a useful tool to predict ionic diffusion and sorption in argillaceous rocks.     

膨润土受热作用后的水-力性能研究

受核废料衰变热影响,处置库内缓冲层的膨润土会长期处于高温状态。经历持续高温作用后,膨润土的膨胀自愈能力能否得以保持,还没有明确的结论。利用马弗炉维持105 ℃恒温环境,对粉状膨润土持续加热到预定周期;然后,获得不同加热周期试样的水-力性能。结果表明,随着加热时间增长,膨润土水-力性能出现大幅衰减。借助X射线衍射仪测试发现持续加热90 d其晶面间距缩合,出现了硅质氧化物胶结,导致颗（团）粒集聚。其红外光谱和热重特征表明,持续加热作用脱去了蒙脱石层间离子水合水,引起部分Na、Mg离子随水分蒸发而逃逸,两者共同作用导致蒙脱石颗（团）粒发生缩合作用。通过观察其扫描电镜图片也能发现,经过90 d持续加热后,蒙脱石颗（团）粒表面不再层次分明,而是紧密地相互搭接,发生了显著的缩合行为。粒度分布特征进一步证实,膨润土经历90 d加热后,即使浸泡28 d,其颗（团）粒依然未被分散,可初步推断上述缩合行为不可逆。     

TDTMA+-柱撑蒙脱石吸附硝基苯的实验研究

以阳离子表面活性剂(十四烷基三甲基溴化铵,TDTMBA)为柱撑剂,在不同浓度条件下(0.2 CEC～2.5 CEC)制备了一系列柱撑蒙脱石,并通过XRD对有机蒙脱石进行表征,研究季铵盐离子在层间的排列结构.同时针对TDTMA -柱撑蒙脱石对硝基苯的吸附进行研究.实验结果表明,吸附去除率受硝基苯的初始浓度、反应时间等因素的影响,而与pH值没有太大的关系.经过柱撑改性后,粘土对硝基苯的吸附能力较原土有了明显的提高.随着层间柱撑浓度的增大,柱撑蒙脱石对硝基苯的吸附量也增大.另外钙基蒙脱石和平卧双层,倾斜单层以及倾斜双层的结构的TDTMA -柱撑蒙脱石对硝基苯的吸附等温线符Freundlich和Langmuir等温方程,假三层结构的TDTMA -柱撑蒙脱石对硝基苯的吸附等温线符合Linear等温方程,这表明前者是以表面吸附为主,后者是以分配作用为主.