Modelling approaches for anion-exclusion in compacted Na-bentonite

The accessible porosity for Cl⁻ in bentonite is smaller than the the total porosity due to anion repulsion (exclusion) by the surface of montmorillonite, the main mineral in bentonite. The accessible porosity is a function of the bentonite density and the salt concentration. Anion exclusion data were gathered from the literature, reprocessed in a coherent data set, and modelled using four different models. Very simple models, with or without anion access to the interlayer space, are successful in reproducing trends in anion exclusion in bentonite as a function of ionic strength in the external solution and montmorillonite bulk dry densities in the bentonite. However, a model that considers clay microstructure changes as a function of bentonite compaction and ionic strength is necessary to reproduce observed trends in the data for all experimental conditions within a single model. Our predictive model excludes anions from the interlayer space and relates the interlayer porosity to the ionic strength and the montmorillonite bulk dry density. This presentation offers a good fit for measured anion accessible porosities in bentonites over a wide range of conditions and is also in agreement with microscopic observations.     

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.     

不同粘土矿物对赖氨酸的吸附行为对比研究

以皂石、高岭石、绿泥石和伊利石为原材料,分别与赖氨酸进行反应,研究赖氨酸在上述粘土矿物上的吸附行为, 并运用粉末X-射线衍射技术（XRD）、傅里叶变换红外吸收光谱术（FTIR）和热重（TG）等分析方法,表征反应前后粘土 矿物的变化。实验结果表明,不同粘土矿物对赖氨酸的吸附等温线均符合Freundlich等温方程,且不同粘土矿物对赖氨酸的 饱和吸附量大小顺序为：皂石>蒙脱石>绿泥石>高岭石>伊利石;XRD结果表明皂石对赖氨酸的吸附发生在矿物层间,而绿 泥石、高岭石和伊利石对赖氨酸的吸附主要在矿物表面进行;FTIR和TG结果表明赖氨酸主要取代粘土矿物层间吸附水,以 氢键的形式与Si-O-Si(IVAl)键合。实验结果将有助于进一步探明环境中粘土矿物对有机质的吸附机理。     

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.     

东太平洋水合物海岭沉积物中黏土矿物与水合物饱和度相关性研究

为了探讨水合物储层中不同黏土矿物与水合物饱和度的关系,选取位于东太平洋水合物海岭国际大洋钻探计划204航次中的3个钻孔(1245B孔、1244C孔和1251B),开展储层沉积物黏土矿物的测试和综合分析。结果表明,蒙脱石、伊利石、绿泥石为主要黏土矿物(平均含量分别为40.3%、33.4%、21.4%);高岭石为次要黏土矿物(平均4.9%)。伊利石、绿泥石、高岭石三种矿物含量的垂向变化规律相似,但它们与蒙脱石的垂向变化趋势相反。该区水合物饱和度与蒙脱石含量呈正相关,且正相关程度在“细粒岩性”层段较高(R=0.55~0.97);水合物饱和度与伊利石、绿泥石、高岭石则显示负相关。3个钻孔中水合物储层厚度、水合物饱和度在各钻孔中分布的差异性表明水合物饱和度的受控因素复杂,首先是气源和流体迁移与供给,其次为沉积物岩性;而“细粒岩性”层段较高含量蒙脱石与水合物饱和度正相关关系可能代表了更次一级的沉积影响因素。为检验其它海区是否也存在黏土矿物对水合物饱和度的影响,将上述3个钻孔与印度外海Krishna-Godavari盆地17-07P钻孔记录进行对比。结果显示,17-07P孔的砂含量高,在粗砂层蒙脱石含量与水合物饱和度呈正相关,反映两个海域岩性对水合物饱和度控制机理不同。上述“细粒岩性”层段蒙脱石含量和伊利石、绿泥石、高岭石3种黏土矿物含量与水合物饱和度之间相关性的差异,可能因为蒙脱石具有特殊层状结构和表面化学性质(层间表面带负电荷、具有可交换的层间水合阳离子等),有利于促进水合物的形成和富集,因而表现为正相关;而伊利石、绿泥石、高岭石自身属性与蒙脱石不同(吸水膨胀能力、对甲烷的吸附能力较蒙脱石弱),不利于水合物的聚集,表现为负相关。     

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.     

钠基蒙脱土水合演化机制

为了查明钠基蒙脱土的水合演化过程,以天然钠基蒙脱土为研究对象,开展在相对湿度（ ）为0～0.98区间的水汽等温吸-脱附试验,通过吸附速率曲线、BET曲线界定钠基蒙脱土各水合阶段及相应的水合主控因素;通过测定晶层 值变化规律,从吸附水影响黏土矿物晶层厚度的角度探讨钠基蒙脱土的水合演化特征;基于傅里叶红外光谱,从水分子结构伸缩振动信息角度对钠基蒙脱土水合演化过程进行定性定量验证;通过热重/差热分析,以吸附水相变所需能量与吸附水重量变化的角度解释钠基蒙脱土的吸附水特征与其水合机制的关系。试验结果表明：在较低相对湿度下（0 0.15）,以钠基蒙脱土矿物外表面吸附为主,形成表面吸附水;0.15 0.40为钠基蒙脱土层间阳离子水合阶段;0.40 0.98,为晶层内外表面水合阶段,水分子逐步完整的包裹蒙脱土,形成多层吸附层。钠基蒙脱土的水合演化过程受控于层间钠离子与晶层基面,层间钠离子的水合能影响了钠基蒙脱土水合演化的起始顺序。     

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。     

十红滩地浸砂岩铀矿层间氧化带蚀变矿物群

十红滩砂岩型铀矿床是我国大型层间氧化带型砂岩铀矿床之一。层间氧化带型砂岩铀矿含矿砂层在含氧含铀水的渗入径流过程中,由于水介质性状的变化,在与砂体发生水岩作用时形成了完全氧化带、不完全氧化带、还原带和原生带等不同地球化学亚带及其相对应的蚀变矿物群,即完全氧化带为褐铁矿(针铁矿、水针铁矿)、伊利石、蒙脱石、少量黄钾铁矾的蚀变矿物群;不完全氧化带为褐铁矿(针铁矿、水针铁矿)、黄钾铁矾、蒙脱石、伊利石、少量绿泥石、高岭石的蚀变矿物群;还原带为沥青铀矿、黄铁矿、高岭石、绿泥石、少量蒙脱石、伊蒙混层粘土、伊利石和碳酸盐等新生蚀变矿物群;原生带的新生蚀变矿物群以黄铁矿、绿泥石、高岭石为主,有时出现少量碳酸盐、蒙脱石和伊利石等。     

西藏伦坡拉盆地渐新世——中新世之交黏土矿物特征及其古气候意义

为揭示伦坡拉盆地渐新世—中新世之交黏土矿物蕴含的古气候信息,探讨其与青藏高原隆升及全球气候响应过程的关系,利用X射线衍射和荧光光谱分析对蒋日阿错剖面的黏土矿物特征进行了深入研究。结果表明:区内泥质岩中黏土矿物以伊/蒙混层矿物为主,伊利石次之,仅含有少量绿泥石和蒙脱石。黏土矿物的垂向组合特征显示伊利石和绿泥石含量在剖面下部低、上部高,伊/蒙混层含量与之相反,伊/蒙混层和伊利石在剖面中部呈明显波动变化,蒙脱石只出现在剖面中下部,可能为区域火山喷发产物在碱性环境中蚀变而成。伊利石结晶度变化于0.24°~0.48°,平均值为0.41°,表明样品未发生明显成岩蚀变,主微量元素比值指示研究区物源位置未发生较大改变,因此研究剖面黏土矿物特征可以有效反映伦坡拉盆地古气候演化过程。根据自生黏土矿物的习性指出伦坡拉盆地在渐新世—中新世之交出现了一次明显的降温事件,并且这次降温在青藏高原内部及周缘地区普遍存在,但造成这次降温事件的根本原因仍值得进一步探讨。     

海洋粘土矿物与颗石藻Emiliania huxleyi共培养的实验研究

颗石藻是海洋中广泛分布的超微型浮游藻,经生物矿化作用形成的碳酸钙质颗石,在古海洋学研究中具有重要意义。海洋粘土矿物与有机质的有机-无机相互作用在全球碳循环中扮演着重要角色。本文选取广泛分布于海洋的赫氏颗石藻Emiliania huxleyi与海洋粘土矿物中具有代表性的伊利石和蒙脱石共培养。通过对颗石藻生长曲线和Sr/Ca、Mg/Ca元素比值、颗石藻与粘土矿物样品的紫外可见光吸收光谱、红外吸收光谱和矿物物相等分析,研究海洋粘土矿物与颗石藻的相互作用规律。通过研究表明伊利石对颗石藻的影响较小,蒙脱石因对营养元素的吸附和颗石藻的絮凝作用对颗石藻的生长和Sr/Ca、Mg/Ca元素比值影响较大。颗石藻代谢分泌的生物分子未能通过层间插层作用进入伊利石层间,颗石藻分泌的生物分子可通过插层作用进入并储存于蒙脱石层间,海洋粘土矿物中的蒙脱石与海洋微生物的相互作用值得地球微生物家关注,可能有助于对古海洋环境的认识。     

Self-diffusion of water and its dependence on temperature and ionic strength in highly compacted montmorillonite, illite and kaolinite

The effect of temperature and ionic strength on the diffusion of HTO parallel to the direction of compaction through 5 highly compacted clay minerals (bulk dry density, ρ_b,d = 1.90 ± 0.05 Mg/m³), namely montmorillonite (Na- and Ca-form), illite (Na- and Ca-form), and kaolinite, was studied. The diffusion experiments were carried out at temperatures between 0 °C and 60 °C and at ionic strengths of 0.01 M and 1 M NaCl for the Na-form clays and kaolinite, and of 0.005 M and 0.5 M CaCl₂ for the Ca-form. The ionic strength had an insignificant influence on the values of the effective diffusion coefficient (variation by less than 10%) for the clays under study at this degree of compaction. The effective diffusion coefficients followed the order Na-montmorillonite < Ca-montmorillonite < Ca-illite < Na-illite  kaolinite. It is thought that the differences between Na- and Ca-montmorillonite originate from the larger size particles, and thus the lower tortuosity of the latter; whereas the differences between Na- and Ca-illite are related to the different degree of solvation of the Na and Ca cations. The activation energies were successfully calculated using the Arrhenius law. Swelling clays (Na- and Ca-montmorillonite) had slightly larger activation energy values (20 kJ/mol) compared to bulk water (17 kJ/mol); Ca-illite (16 kJ/mol), Na-illite (13 kJ/mol) and kaolinite (14.4 kJ/mol) lower values than that of bulk water. The low activation energies of the last three clays may be related to weaker H-bonds between water and the clay surfaces compared to those in bulk water.     

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.     

粘土矿物的掺杂对沉积物吸持Cu、Zn能力的影响

通过考察粘土矿物及掺杂粘土矿物前后沉积物的吸附/解吸特性,分析了伊利石与蒙脱石对重金属污染沉积物中Cu与Zn稳定固定化的可行性。结果表明：伊利石与蒙脱石的掺杂均降低了沉积物吸持Cu的能力（最大下降量分别为5.4%和3.8%）,伊利石的掺杂同样降低了沉积物吸持Zn的能力（最大下降量为4.4%）,但蒙脱石掺杂后沉积物吸持Zn的能力明显增强,最高增加5.7%。因此,蒙脱石具有固定污染沉积物中Zn的能力,但不能提高污染沉积物中Cu的稳定性。     

粘土固体酸的表面酸性调控及其催化活性

固体酸是７０年代末发展起来的一类新型的催化材料,对有机反应具有较强的催化活性,且副反应少,产物易分离,污染少［１］。粘土固体酸是以蒙脱石类粘土为基质材料,通过采用不同的物理或化学方法在不同的条件下调控层间域而制备的,其催化活性和选择性与其表面酸的类型、浓度及强度等有关［２］,为此我们采用离子交换法,以不同类型的阳离子为取代剂,在不同条件下取代交换进入蒙脱石层间,研究制备方法及条件对表面酸性的影响,并考察了催化性能。１　实验部分１－１　原料与试剂钠基膨润土（浙江临安产,主要成分为蒙脱石,用沉降法提…     

Occurrence of Li,B, Cu and Zn in some Egyptian Nile sediments

Lithium, boron, copper and zinc have been determined on cored and surface sediments from the delta and the drainage valley of the Nile River. The clay size fraction separated from the samples consists of montmorillonite and kaolinite as the predominant clay components, followed by illite and chlorite. Quartz and calcite are the non-clay admixtures.Lithium content varies between 7 and 48 ppm in the bulk sediments and between 28 and 61 ppm in the clay fractions, being clearly enriched in the clay material. In the clay fractions, concentration of lithium in kaolinite is indicated by a close relation between the lithium and kaolinite contents and is further supported by a close correlation with A1₂O₃.Boron in the clay fraction (62–112 ppm) appears to be concentrated in detrital illite.The concentrations of copper (26–900 ppm) and zinc (65–333 ppm) in the clay fractions correlate positively with the CO₂ percentage. Both elements tend to occur in or on the claysized grains of caleite.     

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O¹⁸ exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O¹⁸ exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O¹⁸ exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.     

外加直流电场下粘土矿物的膨胀特性研究

实验研究了外加直流电场作用下粘土膨胀率的变化。结果表明,在电场作用下,粘土膨胀率降低,电解膨率大小与粘土性质、电场强度、体相溶液矿化度及施加电场时机等有关。在相同电场强度条件下,膨胀性强的蒙脱石的电解膨率最大,而伊利石、高岭石的电解膨率较小。蒙脱石的电解膨率随着电场强度的增加而增加,当电场强度高于临界值(本实验中为2 V/m)时,电解膨率值基本不变。随着NaCl浓度的增加,蒙脱石的电解膨率以指数规律降低。施加电场时机对电场降低粘土膨胀率的效果有较大影响:在注入蒸馏水的同时施加电场可以有效防止粘土膨胀;在注入蒸馏水之后施加电场可以有效降低粘土膨胀率;先施加低强度电场(EFS=2 V/m)然后再注入蒸馏水,可以造成粘土的膨胀,即使提高电场强度,粘土膨胀率仍然很大。     

Activation energy for diffusion of helium in water-saturated, compacted Na-montmorillonite

It is important to clarify the migration behavior of hydrogen gas dissolved in water-saturated, compacted bentonite, which is a promising material for geologic disposal of high-level waste and TRU waste disposal. The diffusion coefficients of helium, which can be detected under extremely low background conditions, in water-saturated, compacted Na-montmorillonite were determined as a function of temperature by a transient diffusion method. The activation energies for diffusion of helium were then obtained. The activation energies were from 6.9 ± 4.8 to 19 ± 2.8 kJ mol^− 1 and were regarded to be independent of dry density. The activation energies of helium in water-saturated Na-montmorillonite were roughly equal to those in bulk water, 14.9 kJ mol^− 1, and in ice, from 11 to 13 kJ mol^− 1. It is possible that helium diffuses not only in pore water but also in interlayer water.