Stabilization of swelling clays by Mg(OH)2. Factors affecting hydroxy-Mg-interlayering in swelling clays

The damage caused to structures and other human endeavours, on or in the ground, by swelling clay soils is considered as a natural hazard. In order to mitigate this hazard an attempt was made to stabilize the swelling clay mineral structure by the addition of Mg(OH)₂. This will turn the swelling minerals, like montmorillonite, into non-swelling ones, e.g., chloride. Accordingly, the various factors affecting the precipitation-adsorption of the Mg-hydroxide by clays, was investigated, and the conditions giving the best results were established. The factors examined were: the base used as precipitant (NH₄OH and NaOH); the preparation of the precipitate, inside or outside the clay suspension; the sequence and the duration of the reagents addition; the OH/Mg ratio; the time of clay-chemical contact; and the drying time and temperature. The method, was applied to different clay minerals (swelling and non-swelling). The material produced after the Mg-hydroxide precipitation was examined by the methylene blue dye adsorption test, XRD, DTA and DTGA methods; the results were treated statistically by factorial analysis. From the results obtained, it is concluded that the factors affecting the Mg-hydroxide adsorption by clays are: the base used as a precipitant, the preparation of the hydroxide directly inside or outside the clay suspension, the drying temperature, and the rate of titration of the reagents. Therefore, the best conditions for the laboratory preparation of hydroxy-Mg-interlayers are a dilute (1–2%) and well-dispersed clay suspension, pH between 10–12; some 12 meq Mg²⁺, as Mg-salt (e.g., MgCl₂) per gram of clay, added before the base and followed by the dropwise titration of 1–2 N NaOH solution into the clay suspension, to give a molar ratio OH/Mg of about 1.5; vigorous agitation of the suspension during titration of the reagents; centrifugation and decantation of the supernatant liquid, and drying the product at about 250°C. Satisfactory results are also obtained with the fast titration of the base and drying at 105°C to complete dryness.     

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

烃源岩中可溶有机质与粘土矿物结合关系——以东营凹陷沙四段低熟烃源岩为例

 采用超临界抽提(SFE)新技术和氯仿抽提(CE)以及粘土分离等手段对东营凹陷沙四段低熟油烃源岩进行不同处理,得到3种粘土样品:(1)含有机质的粘土原样;(2)氯仿抽提去有机质的样品;(3)不同实验条件下超临界抽提后的样品。然后,分别对这3种粘土样品进行X射线衍射分析(XRD)和傅利叶转换红外光谱分析(FT-IR).研究发现烃源岩中可溶有机质除了吸附于矿物表面外,还吸附于粘土矿物尤其是蒙皂石层的层间,后者主要为碳数相对较低的饱和烃类。这一发现对认识沉积岩中可溶有机质对粘土矿物结构和特性的影响有着重要意义,对烃源岩评价和探讨泥质烃源岩烃类的初次运移提供了新思路。     

Adsorption capacity and mineralogical and physico-chemical characteristics of Shuwaymiyah palygorskite (Oman)

In this paper, Shuwaymiyah palygorskite in the Sultanate of Oman has been characterized mineralogically by X-ray diffraction (XRD) and electron microscopy, chemically by oxide compositions, structural formulae, and cation exchange capacity (CEC), and physically by specific surface area and adsorption isotherms. Batch adsorption studies were performed to evaluate the adsorption performance of methylene blue (MB) basic dye on the local clay mineral. The quantitative XRD analysis indicates that the purity of some selected samples of palygorskite clay is very high (about 70% of the clay minerals are palygorskite and 30% kaolinite). The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images clearly support this conclusion. The adsorption equilibrium revealed that Shuwaymiyah palygorskite clay can uptake up to 51 mg of MB per 1 g mass of clay. MB adsorption is best fitted by Langmuir isotherm, and a pseudo-second-order kinetic model can be efficiently used to predict the kinetic of adsorption of MB by the palygorskite. The results obtained from these laboratory-scale adsorption tests indicate the promising adsorption capability of the Omani palygorskite.     

粘土矿物保存海洋沉积有机质研究进展及其碳循环意义

海洋沉积物吸附有机质的量和有机质循环周期与粘土矿物类型和吸附方式密切相关,并在全球碳循环中扮演着不同的角色。粘土吸附有机质有物理吸附和化学吸附之分,前者主要存在于粘土的微孔隙中,参与年、十年或百年尺度的循环;后者主要存在于粘土矿物层间和外表面,稳定性较好,有机质易于保存,可参与百万年或更长时间的循环,这种不同时间尺度内的碳循环,将会改写海洋沉积物有机碳“源”、“汇”的关系。不同类型粘土矿物的性质存在差异,决定了吸附有机质量的多寡,蒙脱石的吸附量远大于伊利石的吸附量,这可能是造成全球不同海域中有机碳“源”、“汇”变化的原因。海洋沉积物处于水圈、生物圈和岩石圈的交汇地带,有机碳的差异和变化,都会对全球碳循环及气候变化产生重要的影响。     

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。     

Toward the understanding of the treatment of textile industries’ effluents by clay: adsorption of anionic dye on kaolinite

Clays, particularly kaolinite, are promising adsorbents for the treatment of textile effluents, but there is a need of better understanding the mechanisms of adsorption, especially in the case of anionic dyes. Thus, the removal of RR120 anionic dye was investigated using Tunisian raw clay (TBK) composed of kaolinite and illite, and a standard kaolinite (KGa-2), and conducting batch experiments by varying different parameters (contact time, ionic strength, concentration, temperature). We investigated the clays’ surface charges by electrophoretic mobility measures and the dye-clay interactions during adsorption, by the streaming-induced potentials (SIP). The results showed that KGa-2 has higher adsorption capacity for RR120 dye than TBK clay, moreover enhanced by increasing the ionic strength and/or lowering the pH of the aqueous. The SIP results showed an increase of negative charges for both clays, reflecting the adsorption of the anionic dye on the positive charges of the amphoteric surfaces of the clays. The SIP magnitudes indicated a higher adsorption rate for KGa-2 in accordance with the kinetic study. The Sips model that described the best adsorption isotherms indicates lateral interactions of the dye molecules, stronger in the case of KGa-2 than TBK. Also, the dye molecules form a thinner layer on KGa-2 surfaces. In addition, the dye molecule’s structure was not altered, as verified by mass spectrometry. The adsorption process was feasible and spontaneous and favored at ambient temperature. Thus, kaolinite-rich clays are effective in the removal of anionic dyes in aqueous solution and potential good adsorbents in wastewater treatment.     

Thermomechanical model of hydration swelling in smectitic clays: I two-scale mixture-theory approach

A thermomechanical theory of hydration swelling in smectitic clays is proposed. The clay is treated as a three-scale swelling system wherein macroscopic governing equations are derived by upscaling the microstructure. At the microscale the model has two phases, the disjoint clay platelets and adsorbed water (water between the platelets). At the intermediate (meso) scale (the homogenized microscale) the model consists of clay particles (adsorbed water plus clay platelets) and bulk water. At the macroscale the medium is treated as an homogenized swelling mixture of clay particles and bulk-phase water with thermodynamic properties defined everywhere within the macroscopic body. In Part I, the mesoscopic model governing the swelling of the clay particles is derived using a mixture-theoretic approach and the Coleman and Noll method of exploitation of the entropy inequality. Application of this procedure leads to two-scale governing equations which generalize the classical thermoelastic consolidation model of non-swelling media, as they exhibit additional physico-chemical and viscous-type terms accounting for hydration stresses between the adsorbed fluid and the clay minerals. In Part II the two-scale model is applied to a bentonitic clay used for engineered barrier of nuclear waste repository. The clay buffer is assumed to have monomodal character with most of the water essentially adsorbed. Further, partial results toward a three-scale thermomechanical macroscopic model including the bulk phase next to the swelling particles are derived by homogenizing the two-scale model with the bulk water. A notable consequence of this three-scale approach is that it provides a rational basis for the appearance of a generalized inter-phase mass transfer between adsorbed and bulk water. Copyright © 1999 John Wiley & Sons, Ltd.     

Modified Darcy''s law, Terzaghi''s effective stress principle and Fick''s law for swelling clay soils

Governing equations often used in soil mechanics and hydrology include the classical Darcy's law, Terzaghi's effective stress principle, and the classical Fick's first law. It is known that the classical forms of these relations apply only to non-swelling, granular materials. In this paper, we summarize recent generalizations of these results for swelling porous media obtained using hybrid mixture theory (HMT) by the authors. HMT is a methodical procedure for obtaining macroscopic constitutive restrictions which are thermodynamically admissible by exploiting the entropy inequality for spatially-averaged properties. HMT applied to the modeling of swelling clay particles, viewed as clusters of adsorbed water and clay minerals, produces additional terms necessary to account for the physico-chemical forces between the adsorbed water and clay minerals or, more generally, for swelling colloids. New directions for modeling consolidation of swelling clays are proposed based on our view of clay particles as a two-phase system.     

Physicochemical characteristics for adsorption of MTBE and cadmium on clay minerals

Physicochemical characteristics relevant to the adsorption of MTBE and Cd on three types of clay minerals were investigated. The characteristics were examined through batch adsorption tests conducted under various experimental conditions such as adsorption time, ratio of solution-to soil, concentration of solutes, concentration of organic matters, pH, and zeta potential. The adsorption efficiency of MTBE or Cd on three types of clays decreased in response to an increase of the ratio of solution-to-soil; nevertheless, the adsorbed amounts inversely increased. MTBE was adsorbed on clays in an increasing order of vermiculite, bentonite, and CTAB-bentonite. However, Cd was adsorbed in a different order of bentonite, vermiculite, and CTAB-bentonite. The adsorption of MTBE was well fitted with the Freundlich model, whereas the Cd was more closely suited to a Langmuir equation. By adding humic acids of 1 and 5%, MTBE was significantly adsorbed on bentonite and vermiculite, respectively, but beyond that, its adsorption was diminished. In comparison, the adsorption on CTAB-bentonite was increased in proportion to the humic acids addition. Likewise, the addition of humic acids acted to increase the adsorption of Cd regardless of the types of adsorbent, where up to 90% of Cd was removed at pH 10. Further increase of pH declined the degree of zeta potential, while increasing Cd concentration also lowered the zeta potential, which consequently contributes in enhancing the adsorption efficiency of Cd on clays.     

Chemical processes affecting alkalis and alkaline earths during continental weathering

The alkali and alkaline earth concentrations in the Toorongo Granodiorite weathering profile are controlled by two competing processes; leaching of cations from primary minerals during their degradation to clays; fixation, by exchange and adsorption, of the same cations onto the secondary clay minerals. Degradation and leaching dominate the early weathering stages whereas during the advanced stages, exchange and adsorption onto clays are of most influence.The alkali and alkaline earth compositional changes in the Toorongo Granodiorite weathering profile are typical of changes occurring during weathering of the continents, consequently the following generalizations apply to continental weathering. Ca, Sr and Na are most rapidly and most strongly removed (as dissolved species) during weathering of fresh continental rocks. Although large quantities of Mg are transported to the marine environment as dissolved species, appreciable amounts remain (fixed in secondary clay minerals) at the weathering site to be removed during mass wasting of continental weathering profiles. Large quantities of Rb, Cs and Ba, fixed in continental weathering profiles by exchange and adsorption onto secondary clays, are transported from the continents only during mass wasting of the continents.     

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。     

烃源岩中可溶有机质与粘土矿物结合关系——以东营凹陷沙四段低熟烃源岩为例

采用超临界抽提(SFE)新技术和氯仿抽提(CE)以及粘土分离等手段对东营凹陷沙四段低熟油烃源岩进行不同处理,得到3种粘土样品:(1)含有机质的粘土原样;(2)氯仿抽提去有机质的样品;(3)不同实验条件下超临界抽提后的样品。然后,分别对这3种粘土样品进行X射线衍射分析(XRD)和傅利叶转换红外光谱分析(FT-IR).研究发现烃源岩中可溶有机质除了吸附于矿物表面外,还吸附于粘土矿物尤其是蒙皂石层的层间,后者主要为碳数相对较低的饱和烃类。这一发现对认识沉积岩中可溶有机质对粘土矿物结构和特性的影响有着重要意义,对烃源岩评价和探讨泥质烃源岩烃类的初次运移提供了新思路。     

Methane Adsorption on Montmorillonite,Kaolinite and Illite at High Pressures

Shale gas, which is derived from organic matters in shale and stored in shale deposits, is an important unconventional gas resource and attracts attention due to its significant requirement in the hydrocarbon production. Methane (CH4) is the dominant component of shale gas, and adsorbed gas is an important reservoir form. Many studies have investigated the adsorption capacities and adsorption mechanisms of CH4 in shale. Organic matters and clay minerals have been proposed to be the two major components for CH4 adsorption. Adsorption of CH4 in organic matters, such as the adsorption capacity and effects of characteristics of the organic matters, has been well investigated. However, studies on CH4 adsorption on clay minerals have mainly focused on evaluating the adsorption capacity, and very little information about the adsorption mechanism has been provided. For example, the adsorption sites and factors influencing CH4 adsorption on clay minerals remain unclear. Three main reasons account for this: (1) the co-existence of organic matters in samples affects the evaluation of CH4 adsorption on clay minerals; (2) the pressures used during adsorption are not representative of actual reservoir pressures; and (3) the clay minerals selected have low swelling capacity and a smaller interlayer distances than a CH4 size, resulting in the misunderstanding of the CH4 adsorption sites.     

Rare earth elements in Quaternary clays of the Numedal area, southern Norway

Rare earth elements (REE) in the clay fraction (< 2μ) of the Quaternary deposits in the Numedal area, southern Norway, have been determined by a spark source mass spectrometric method. The REE content was studied in relation to weathering and sedimentological factors.

The total REE content varies from 100 to 1300 ppm. An average of the similar fraction of 16 non-marine clays, mostly tillitic, gave 527 ppm REE. An average of 38 glacial and postglacial marine clays from the lower part of the Numedal valley gave 335 ppm REE (max. 781 ppm). After removal of adsorbed ions the average total REE content of morainian and marine clays decreased to 186 ppm.

The content and distribution of the REE in the Numedal clays are strongly influenced by environmental factors. Under neutral and alkaline conditions the REE are accumulated by adsorption on clay minerals, and by increasing the hydrogen ion concentration the adsorbed ions are readily removed.     

陕南黑木林纤维水镁石矿地质特征及应用前景浅析

黑木林纤维水镁石矿是目前全球范围内已知的最大纤维水镁石矿床,赋存于加里东期侵入的超基性岩——斜方辉石橄榄岩中,该岩体已完全蛇纹岩化.矿体平均厚度约400m,长2400m,平面形态呈一长的透镜状.纤维水镁石平均品位4.322％.纤维水镁石是水镁石的变种矿物.纤维水镁石矿物呈纤维状或片状集合体,成分接近于水镁石理论值.属三...     

有机粘土的特性及其对肥料养分的缓释作用

本研究表明 ,表面活性剂 2号不仅可以吸附在蒙脱石、高岭石和凹凸棒石的表面上 ,还可进入蒙脱石的层间 ,将其晶层撑开 ,并以双层小于 65°角斜交于蒙脱石的晶片之间 ,同时有极少量的表面活性剂 2号以单层方式直立于晶片上 ,形成石蜡质构型。由于粘土矿物对表面活性剂 2号的吸附作用 ,使其热性质发生变化 ,去除吸附水的温度降低并出现放热峰。此外 ,还使得有机粘土的含水量和吸湿率较原土有显著降低。有机粘土应用于肥料工业的复混肥生产中 ,不仅可以使其有效成粒率提高 3 0 % ,还可使其养分释放具有显著的缓释效果。     

Engineering characteristics and environmental impacts of the expansive Ankara Clay,and swelling maps for SW and central parts of the Ankara (Turkey) metropolitan area

Volume-changing clay soils constitute the most costly natural hazard to buildings on shallow foundations. With the existing expansive clays in Ankara, low-rise buildings at the southwest part of the city have shown damage resulting in considerable maintenance costs. This paper reports the findings of an experimental investigation emphasizing the swelling behavior of Ankara Clay and correlations between the swelling parameters and other soil properties, and present a synthesis of observed damage details. The poor performance of the affected light-weight structures is assessed in the light of environmental conditions. In addition, swelling maps for SW and central parts of the Ankara metropolitan area, based on measured and predicted swelling parameters, are constructed for the purposes of land-use planning and general assessment of environmental problems. The experimental results suggest that the clay has high-to-very high activity, depth of active zone generally ranges between 1–2 m, the use of remolded and desiccated specimens seems to be a better approach in swelling tests, and the empirical equations based on two or more index or physical properties are good predictors for the estimation of the swelling potential of the clay. High swelling pressures exerted by the soil, flat topography and poor drainage, climatic conditions and poor construction methods are the main reasons of the structural damage observed at the study site.