粘土矿物钝化改性和钝化机理初步研究

在岩土工程中,进行灾害防治和软基处理的一个核心问题是把粘土矿物由亲水性改造成疏水性,抑制和降低其含水量,使得粘土遇水后不再吸水膨胀,从而保持土壤的稳定性。岩土力学工程中以保持土壤稳定性为目的对粘土的改性称为“钝化”。所谓钝化就是用 钝化剂与粘土矿物表面发生反应,改变粘土矿物的表面结构,提高憎水性,增加粘土整体的力学性质,从而达到稳定土体的目的。在粘土矿物钝化中表面活性剂是一个重要的组成部分 ,但是表面活性剂在固液界面的吸附,除决定于其本身的性质外,还决定于固体的性质、溶 液的pH值和温度等。因此,研究粘土矿物表面结构和性质以及与钝化剂的相互作用是提高粘 土矿物钝化效果的重要途经。利用近代分析方法（XRD、IR、Raman、MAS NMR、TEM、AFM和S EM）,对粘土矿物（高岭石、蒙脱石和伊利石）钝化前后的表面结构和性质进行了系统研究 ,并结合相关的土力学、工程力学参数的测定,阐明粘土矿物钝化的机理,剖析和研制粘土 矿物钝化剂,为解决各类工程和灾害问题中的土壤稳定提供理论依据。     

Surfactant-enhanced remediation of contaminated soil: a review

Extracting aqueous solutions with or without additives are employed to solubilize contaminants in soil. Since water solubility is the controlling removing mechanism, additives are used to enhance efficiencies. These additives can reduce the time to treat a site compared to the use of water alone. Additives must be of low toxicity and biodegradable. The research in this area has focussed mainly on halogenated volatile organic compounds (VOCs) and is still quite limited for metal removal. Additives include surfactants, organic and inorganic acids, sodium hydroxide, which can dissolve organic soil matter, water-soluble solvents such as methanol, displacement of cations with nontoxic ones, complexing agents such as EDTA, acids in combination with complexing agents or oxidizing/reducing agents. Cationic, anionic and nonionic surfactants are particularly used for soil washing or flushing. They contain both hydrophobic and hydrophilic portions, making them ideal for solubilization of hydrophobic compounds. Numerous studies have indicated that surfactants enhance recoveries of non-aqueous phase liquids (NAPLs). There have also been indications that pretreatment of soil with surfactant washing to solubilize hydrophobic compounds such as PAHs enhances biodegradation of these contaminants. A few in situ field studies have been performed with surfactants. Large-scale treatment has been done mostly for organic removal. Soil pH, soil type, cation exchange capacity (CEC), particle size, permeabilities and contaminants all affect removal efficiencies. High clay and organic matter contents are particularly detrimental. Understanding the chemistry of the binding of the contaminant and the hydrogeology of the site are very important. Once the water is pumped from the soil, it must be extracted and then treated to remove the hydrocarbons and metals. Several technologies exist such as sodium hydroxide or sodium sulfide precipitation, ion exchange, activated carbon adsorption, ultrafiltration, reverse osmosis, electrodialysis and biological processes. Recycling of the surfactants is desired to decrease treatment costs.

This paper will provide an overview of the laboratory research, field demonstration and full-scale application of surfactants for the remediation of contaminated soil. The majority of pilot scale in situ flushing tests, particularly in the United States, have involved the use of surfactants and co-solvents. There are only a few full-scale projects however. Recent laboratory scale efforts by the authors concerning the use of biosurfactants, biologically produced surfactants, to enhance the removal of copper, cadmium and zinc from contaminated soils and sediments are discussed. Three types of biosurfactants were evaluated for their effectiveness. They included a lipopeptide called surfactin from Bacillus subtilis, a rhamnolipid from Pseudomonas aeruginosa and a sophorolipid from Torulopsis bombicola. The results indicated the feasibility of removing the metals with the anionic biosurfactants even though the exchangeable fractions were not significant.     

蒙脱石中性化改性实验研究

使用表面活性剂HDTMAB对含有蒙脱石等粘土矿物的膨润土进行不同程度的有机改性,并利用自由膨胀率的实验方法定量描述改性膨润土在水以及甲苯介质中的膨胀规律。对实验结果进行数学分析后发现,随着改性剂用量的加大,改性膨润土在水介质中的自由膨胀率明显降低,而在甲苯介质中的自由膨胀率显著上升,当改性剂用量约为15%时,改性膨润土在水以及甲苯介质中都没有发生剧烈膨胀。依照上述膨润土的改性方法,对胜利油田提供的岩心样品进行了有机改性,并得到了相同的规律。由此得出,严格控制改性剂用量可以实现蒙脱石的中性化改性。利用这一规律,将适量的改性剂注入地下,既能够缓解油气田储层中蒙脱石的水敏膨胀危害,又不会造成过量的油脂分子吸附于矿物表面。     

有机粘土化学研究进展与展望

有机粘土化学是研究粘土矿物与有机化合物之间相互作用的一门学科,其内容包括粘土矿物对有机化合物的吸附作用,粘土矿物对有机化合物转化的催化作用以及有机化合物对粘土矿物的合成与风化的影响。着重阐述了近20年来有机粘土化学的研究进展,并就这一学科领域的研究作了展望。     

粘土矿物对形成过渡带气的催化作用研究

本文分析了有机质在粘土矿物中的赋存状态，测定了粘土矿物的表面酸、实验模拟了低演化程度的烃源岩及其抽提物干酪根＋不同粘土矿物的催化机制、并通过粘土催化醇脱水反应对粘土过渡带有机质成气机理进行了探讨。研究结果表明，过渡带气的形成主要是受蒙脱石粘土矿物的催化所致，其原因是成岩过程中蒙脱石向混层矿物转化在蒙脱石晶间发生大量的铝代硅，因此在粘土表面产生电荷不平衡而形成酸性，井以路易斯酸和布郎酸作用于有机质，使碳－碳键发生断裂以形成气态烃。     

Separation of Clay Minerals from Host Sediments Using Cation Exchange Resins

Classic physical and chemical treatments applied to separating clay minerals from the host sediments are often difficult or aggressive for clay minerals. A technique using cation exchange resins (amberlite IRC-50H and amberlite IR-120) is used to separate clay minerals from the host sediments. The technique is based on the exchange of cations in the minerals that may be associated clay minerals in sediments, such as Ca and Mg from dolomite; Ca from calcite, gypsum and francolite with cations carried by resin radicals. The associated minerals such as gypsum, calcite, dolomite and francolite are removed in descending order. Separation of clay minerals using cation exchange resins is less aggressive than that by other classic treatments. The efficiency of amberlite IRC-50H in the removal of associated minerals is greater than that of amberlite IR-120.     

Surfactants enhanced recovery of endosulfan from contaminated soils

Soil pollution due to hydrophobic organic compounds is a wide environmental problem. Extensive use of endosulfan in cotton and paddy to meet the needs of the growing population has led to contamination of soil and other ecosystems. Endosulfan is hydrophobic, highly toxic to aquatic and human population and persists in soil for more than a year. To overcome the problem of hydrophobicity and limited availability, surfactants play a major role in soil remediation. In the present study, the potential of non-ionic synthetic surfactants (Tween 80, Triton X-100) and biosurfactant (Surfactin produced by Bacillus subtilis) for enhancing the release of endosulfan from contaminated agricultural soils was evaluated using the batch method. Incorporation of the surfactant concentrations at above Criticle Miceller Concentration (0.5, 1 and 2 g/L) into soil enhances the release of endosulfan. Surfactin produced from Bacillus subtilis recorded maximum (91.5%) recovery. The observed order of recovery being surfactin > Tween 80 > Triton X-100. The result suggest that surfactants could help in the remediation of soils polluted by pesticides.     

利用扫描电镜和X射线衍射仪对滑坡滑带土的研究

利用扫描电子显微镜（SEM）和X射衍射仪（XRD）研究了三峡库区，黄河小浪底等地40个滑坡滑带土的结构及物质组合，指出当滑坡处于滑动阶段时，滑带土表居可见粘土矿物定向排列，普遍可见擦痕（弧型，线型，紊乱型），微裂隙和微空隙发育，微生物较多，当斜坡处于稳定阶段时，岩层软弱带可见粘土矿物无定向排列，表面无擦痕，常见树枝状结构。滑带土的物质组合主要为：蒙脱石，蛭石，伊利石，高岭石，绿泥石，方解石，石英，长石和微生物，而蒙脱石，蛭石和微生物含量是滑坡滑动的一个重要因素。据微结构的变化和物质组合可以分析滑坡的活动次数，活动阶段和形成机理，为滑坡治理和稳定性评价提供依据。     

粘土矿物的环境意义

粘土矿物在沉积和埋藏作用过程中可发生转变。它的形成和转化与其所处的环境有密切关系 ,因此深入研究粘土矿物的组合与含量的变化、结构特点与转化规律以及粒度分布等特征 ,可以推测其形成区和来源区的风化作用类型和气候演变规律 ,有助于揭示全球性的环境演变规律。对粘土矿物的大量研究所揭示的古气候环境演变的信息 ,已被用于重建古气候和恢复大陆古环境。此外 ,由于粘土矿物具有较强的吸附性、离子交换性和膨胀性 ,对水体中各种类型的污染物有良好的吸附性能 ,并使土壤有一定的自净作用 ,所以在环境污染的防治中有广阔的应用前景。     

Enhanced biodegradation of polycyclic aromatic hydrocarbons using nonionic surfactants in soil slurry

The effect of nonionic surfactants on the solubility and biodegradation of polycyclic aromatic hydrocarbons (PAHs) in the aqueous phase and in the soil slurry phase, as well as the fate of these surfactants, were investigated. The PAH solubility was linearly proportional to the surfactant concentration when above the critical micelle concentration (CMC), and increased as the hydrophile–lipophile balance (HLB) value decreased. Substantial amounts of the sorbed phenanthrene in the soil particles were desorbed by non-ionic surfactants into the liquid phase when the ratio of soil to water was 1:10 (g/ml). Brij 30 was the most biodegradable surfactant tested, showed no substrate inhibition up to a concentration of 1.5 g/l, and was definitely used as a C source by the bacteria. Naphthalene and phenanthrene were completely degraded by phenanthrene-acclimatised cultures within 60 h, but a substantial amount of naphthalene was lost due to volatilization. The limiting step in the soil slurry bioremediation was bioavailability by the micro-organisms for the sand slurry and mass transfer from a solid to aqueous phase in the clay slurry.     

Effect of Clay Minerals on Transport of Surfactants Dispersed Multi-walled Carbon Nanotubes in Porous Media

Clay minerals can hinder the transport of various contaminants in soil and aquifer, but how clay minerals affect the transport of nanoparticles in aquifers has not been investigated in depth. In this paper, the transport of surfactants dispersed multi-walled carbon nanotubes (MWCNTs) in well-defined quartz sand and mixtures of quartz sand and clay minerals (kaolinite and montmorillonite) with varying ionic strengths was studied. Sodium dodecyl benzenesulfonate (SDBS) and octyl-phenol-ethoxylate (TX100) MWCNT suspensions can migrate through quartz sand easily, but the presence of less than 2% w/w clay minerals in quartz sand can significantly hinder the transport of MWCNT suspensions, especially at high ion strength (0.6 mM CaCl2). The inhibition mechanism of clay minerals for surfactant-dispersed MWCNTs in porous media is the interception of MWCNTs. Kaolinite has stronger inhibition effect for MWCNTs transport than montmorillonite because more kaolinite can be retained in the quartz sand. Adsorption of surfactants by clay minerals does not affect the transport of MWCNTs significantly. This finding is important for the environmental assessment of MWCNT transport risks in soils and aquifers.     

粘土矿物在黄河源区古气候研究中的应用

沉积物中粘土矿物的组成具有一定的古气候指示意义。利用沉积物中粘土矿物的组成探讨了黄河源区全新世的古气候变迁。通过X衍射方法分析了一个全新世地层剖面的粘土矿物类型和含量的变化,这些粘土矿物主要由伊利石、伊蒙混层矿物和少量的高岭石、绿泥石组成。对粘土矿物含量变化的分析和对比研究表明,黄河源区在全新世的气候寒冷干燥,即使在大暖期也显得温凉。全新世的气候演变可划分为3个阶段,即早全新世的干冷期、中全新世的温凉期(大暖期)和晚全新世的干冷期。在大暖期,在7 0kaB P 和5 0kaB P 前后发生了两次较强的降温事件。     

黏土矿物组构对水化作用影响评价

泥页岩水化过程中黏土矿物起着主要的作用,但目前还缺少相关的定量描述研究。为此,利用SEM、X-粉晶衍射技术,对采自不同地区的泥岩和板岩在干燥状态、不同浸泡时间后的微观结构和含量进行分析及研究,分析黏土矿物的组构随浸泡时间的变化过程,并定量地分析其对水化过程的影响规律,研究泥页岩的软化过程。研究认为,（1）泥页岩、板岩中影响水化过程的内在因素是蒙脱石、高岭石、绿泥石和伊利石等黏土矿物的含量;（2）黏土矿物定向排列时水化作用效果较无序排列时的明显;（3）泥页岩的水化作用是一个渐进的过程,即在水化过程中流体介质首先使表面的黏土矿物软化,产生掉块;随着时间延长,流体沿裂缝、层理面向岩石内部渗透,黏土土矿物发生膨胀;无围岩限制作用时坍塌掉块持续发生;（4）泥浆中加入一定的无机盐有助于抑制水化过程的发生;压力增加将抑制水化过程的产生;温度升高则能促进泥页岩的水化过程。     

粘土矿物对古气候指示作用浅析

由于粘土矿物的成分、组合、含量以及结晶度的变化可以反映母源区气候冷、暖周期性变化，因此利用粘土矿物重建古气候环境近年来得到广泛的应用。然而，由于粘土矿物的敏感性，其气候记录的信息往往会被其他影响因素(如母源区、沉积环境、成岩作用等)掩盖。因此，在利用粘土矿物重建古气候环境时，需要综合考虑气候以及非气候的各种影响因素。     

ETM+和ASTER数据在遥感矿化蚀变信息提取应用中的比较——以安徽铜陵凤凰山矿田为例

在利用遥感技术找矿中,矿化蚀变信息识别与提取起着重要作用。选择具有典型蚀变特征的安徽铜陵凤凰山矿田作为研究区,从分析地物波谱,尤其是岩矿光谱特征出发,根据ETM+和ASTER数据的光谱特征,采用主成分分析（PCA）,设计了相应的粘土矿化蚀变信息提取方案,成功地进行信息提取。对两者的提取结果进行比较后表明,ASTER数据较之ETM数据在粘土类矿化蚀变信息提取中具有更大的优势。     

不同产地矿物对有机-钛柱撑蒙脱石复合材料光催化活性的影响

以钛酸丁酯为前驱体,采用醋酸为酸催化剂制备TiO2溶胶,将制备的溶胶分别加入经表面活性剂十六烷基三甲基溴化铵改性的河北、临安、安吉、内蒙古膨润土中,制备有机-钛柱撑膨润土复合光催化剂,并对其进行XRD、SEM、BET表征。结果表明,TiO2插入了膨润土层间,并以锐钛矿型的晶形存在,制备的复合光催化剂仍有较好的层状结构,其比表面积均比相对应的不同产地的膨润土的比表面积大。以甲基橙为目标污染物,考察了有机-钛柱撑膨润土复合光催化剂的吸附性能和光催化活性,发现所制备的复合光催化剂具有较好的光催化活性,而且用不同的膨润土合成的催化剂的光催化活性差别很大。膨润土的化学组成和层状结构上的差异是复合催化剂吸附性能和光催化活性差别的主要原因。其中有机-钛柱撑临安膨润土复合光催化剂的光催化活性最好。     

Enhancing the Adsorption Capacity of TMA-montmorillonite Toward HOCs

Organoclays synthesized with small organic cations can effectively adsorb hydrophobic organic compounds (HOCs), and the hydrophobic siloxane surfaces of clay minerals have been considered as the main adsorption sites for HOCs. Therefore, reducing charge density of clay minerals which can effectively increase the exposed siloxane surface areas has been generally used to enhance the adsorption capacity of organoclays towards HOCs. In this work, we will present a new method to increase the exposed siloxane surface areas of the synthesized organoclays and enhance their adsorption capacity. Firstly, the original inorganic cations on montmorillonite were exchanged with Li+, and then part of the Li+ (i.e., 20% to 60% of the montmorillonite’s CEC) were further exchanged with tetramethylammonium cation (TMA). After that ,the samples were heated at 200 ℃ for 12 h to make sure most of the Li+ were transferred to montmorillonite layers. With this method the layer charge of montmorillonite can be effectively reduced while the layered structure of montmorillonite will be preserved by pre-exchanged TMA. Finally, the remaining Li+ cations were further exchanged with TMA. The structural and adsorptive characteristics of the resulting organoclays were compared with those synthesized using traditional method (i.e., first reducing the charge density and then exchanging TMA).     

The association of organic molecules with clay minerals in aqueous solutions

The uptake of dissolved organic molecules by kaolinite and montomorillonite clay minerals was measured in distilled water and saltwater solutions. Glucose and valine exhibited low affinities for both clay minerals over a wide range of concentrations in distilled water and seawater solutions. Stearic acid was efficiently removed by both clay minerals from all solutions over the concentration range 10–1000 ppb. These experiments suggest that some dissolved organic molecules may be preferentially removed by clay minerals in natural waters. It is unlikely, however, that the partitioning of simple organic molecules between natural waters and suspended clay minerals could produce the high concentrations of organic matter that occur in most fine-grained sediments.     

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。     

Distribution of clay minerals in surface sediments of the Aegean Sea: a compilation

Extensive published data sets and some new data on the clay mineral composition of surface sediments in the Aegean Sea, northeastern Mediterranean Sea, have been compiled in order to map the distribution patterns of clay mineral assemblages and to decipher source areas and transport paths. We distinguished six provinces, a Northwest Aegean Province, a Marmara-Dardanelles Province, a West Turkey Province, a Southeast Aegean Province, a Kithira Province and a Central Aegean Province. The clay mineral assemblages in the coastal and shelf areas carry the signature of the riverine sediment discharge from southeast Europe and Turkey, respectively. The southern Aegean Sea is probably influenced by the River Nile discharge and transport of clay minerals by surface currents. The clay minerals in the central Aegean Sea form a mixed assemblage comprising components of the other assemblages. A dispersion and dilution of clay minerals by surface currents is obvious.