蒙脱石等粘土矿物对重金属离子吸附选择性的实验研究

矿物质与重金属离子间的相互作用已是当今环境科学、矿物学,土壤化学等学科领域研究的热点。通过蒙脱石,伊利石和高龄石在一定的介质条件下对Ｃｕ＾２＋、Ｐｂ＾２＋、Ｚｎ＾２＋、Ｃｄ＾２＋、Ｃｒ＾３＋五种重金属离子的竞争吸附实验研究,阐明了三种粘土矿物对五种重金属离子的吸附选择性。     

蔚县煤田泥质岩的粘土矿物组成及其地质意义

通过x射线衍射曲线和扫描电镜研究，揭示出蔚县煤田煤煤系泥质岩粘土矿物中的高岭石主要为来自基底灰岩风化壳，少量为盆地内生成，伊利石有从剥蚀区搬运来的，也有由蒙脱石和高岭石转化而成的，蒙脱石则主要属盆地自生并与中基性火山物质有直接关系，分别反映了酸性冲洪积，酸－弱碱性沼泽，河一湖及偏碱性干旱冲洪积环境。     

氧化铁矿物对五氯苯酚表面吸附实验及其反应模式

批量法实验研究表明,五氯苯酚 (PCP)在合成的针铁矿、纤铁矿和赤铁矿表面吸附的浓度等温线为饱和型特征,可用 Langmuir公式拟合,而 pH吸附等温线为峰型曲线,峰值在 pH≈ 5. 矿物表面化合态和 PCP溶液离子化合态分析与计算表明, PCP在氧化铁矿物表面存在两种吸附反应模式,即表面静电吸附反应和表面络合吸附反应,表面静电吸附反应常数比表面络合吸附反应常数高 1～ 2个数量级.并进一步从反应机制上证明了憎水型可离解有机化合物 (HIOCs)在矿物表面吸附的模式与趋向性.     

五氯苯酚在矿物表面吸附——实验、表面反应模式及其环境意义

利用批量平衡技术研究了石英、高岭石、伊利石、蒙脱石和铁氧化物对五氯苯酚(PCP)吸附的pH关系等温线和浓度关系等温线,发现所有矿物的pH关系等温线都表现出典型的峰形曲线特征,峰位在pH=5～6之间,依矿物不同而不同。基于矿物表面羟基位化合态和PCP的化合态考虑,提出一种包含表面络合反应和表面静电吸附反应的模式,对pH关系等温线计算拟合发现有很好的相关性。模式计算还表明,石英和层状硅酸盐矿物对PCP吸附以表面络合反应为主,而氧化铁矿物则包含表面络合反应和表面静电吸附反应,但以后者占主导,其反应平衡常数比前者大1～3个数量级。高岭石和氧化铁矿物的浓度吸附等温线可用Langmuir方程很好拟合,最大吸附量的大小顺序是赤铁矿>纤铁矿>针铁矿>高岭石>石英>蒙脱石≈伊利石,并可以用矿物表面羟基位浓度和反应机制加以解释。PCP在矿物表面可观的吸附量说明矿物表面吸附对憎水性可离解有机化合物(HIOCs)在天然水相体系和沉积中的迁移转化过程起着相当重要的作用。     

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。     

五氯苯酚在氧化物和粘土矿物表面吸附:表面反应模式及其环境意义

石英、高岭石、伊利石、蒙脱石和铁氧化物对五氯苯酚(PCP)吸附的pH关系等温线和浓度关系等温线已用批量平衡技术进行研究。所有矿物的pH关系等温线都表现出典型的峰形曲线特征,峰位在pH=5~6之间,依矿物不同而不同。基于矿物表面羟基位化合态和PCP的化合态考虑,研究提出一种包含表面络合反应和表面静电吸附反应的模式,对pH关系等温线计算拟合发现有很好的相关性。模式计算还表明,石英和层硅酸盐矿物对PCP吸附以表面络合反应为主,而氧化铁矿物则既包含表面络合反应,又包含表面静电吸附反应,但以后者占主导,其反应平衡常数比前者大1~3个…     

粘土矿物对胡敏酸的吸附行为研究

以蒙脱石和高岭土为吸附剂,分别与胡敏酸反应,研究胡敏酸在蒙脱石和高岭石上的吸附行为,并运用红外光谱、热重和Zeta电位等分析方法,表征分析了吸附前后的粘土矿物.实验结果表明,吸附过程受胡敏酸的初始浓度和pH值等因素影响;胡敏酸对粘土矿物的吸附等温线符合Freundlich等温方程;表征分析表明两种粘土矿物与胡敏酸复合体的红外光谱出现了C-H振动吸收峰;粘土矿物与胡敏酸结合后Zeta电位下降.实验的结果将有助于进一步探明环境中粘土矿物对胡敏酸的吸附机理.     

镉在蒙脱石等粘土矿物上的吸附行为研究

研究了土壤中主要硅酸盐粘土矿物蒙脱石、伊利石、高岭石、海泡石对重金属镉的吸附行为.结果表明:硅酸盐粘土矿物吸附镉受酸度和离子强度的影响;吸附反应是快反应,能很好地符合Lagergren二级吸附速度方程;优化条件下的高岭石对镉吸附很弱,蒙脱石、伊利石、海泡石对镉的实验饱和吸附容量分别为2.88、1.08、2.82 mg/g,蒙脱石吸附镉更适合Freundlich拟合,伊利石、海泡石对镉的吸附结果更适合Langmuir拟合;相关性分析表明,硅酸盐粘土矿物对镉的饱和吸附容量大小与其理化性质有关,其中矿物中氧化锰含量高低与其对镉饱和吸附容量大小的相关性达到极显著水平.     

粘土矿物对金属镉的吸附与解吸研究

通过以2:1型膨润土、1:1型高岭土为代表的粘土矿物吸附金属元素Cd和以醋酸、草酸和柠檬酸为代表的有机酸对粘土矿物吸附金属Cd的解吸作用研究,得出结果:粘土矿物对镉离子的吸附率随Cd浓度增大而下降;2:1型膨润土的吸附能力大于1:1型高岭土;三种弱酸对粘土矿物吸附的镉离子具有一定的解吸附能力,其中柠檬酸>草酸>醋酸,且对膨润土的解吸效率低于对高岭土的解吸效率.     

Adsorption of Pentachlorophenol onto Oxide and Clay Minerals： Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.     

Copper-bearing clay minerals of the oxidized zone of the Rakha-Chapri Block,Singhbhum Copper Belt,India

In the oxidized zone of Rakha-Chapri Block of the Singhbhum Copper Belt, alteration of biotite, chlorite and muscovite extends down to ∼ 60 m. Below this level, these minerals are not altered, implying a supergene origin for the clay alteration products. The altered host-rock profile consists of an upper, predominantly kaolinitic zone and a lower illite-chlorite rich zone, with the clay minerals showing an overall tendency to decrease with depth. Kaolinite is the dominant clay mineral, the proportion of which varies considerably with depth, and chlorite, illite and halloysite are the other clay minerals of the oxidized zone. Incipient removal of copper even from the cap rocks, in-situ transformation of sulphides to oxidized compounds, and the unusual mode of occurrence of copper in the oxidized zone are the characteristic features of the Rakha-Chapri Block. Insufficient localized hydrolysis of silicates is considered responsible for relatively low acidity in the oxidized zone as a whole. Copper forms a component of the clay minerals probably as surface adsorbed or/lattice-bound ions.     

蒙脱石、高岭石、伊利石对重金属离子吸附容量的实验研究

在pH=4,t=23℃和微量浓度条件下,不改变离子浓度,通过增加吸附液体积进而增加体系中重金属离子含量的方法进行了蒙脱石、伊利石、高岭石对Cu2+、Pb2+、Zn2+、Cd2+、Cr3+等重金属离子吸附容量的实验研究,结果表明,3种矿物吸附容量大小顺序为蒙脱石>伊利石>高岭石,与其阳离子交换容量密切相关.Cu-蒙脱石和Cr-蒙脱石的X射线衍射结果表明,Cu2+、Cr3+通过离子交换作用进入了蒙脱石的层间.同一矿物对不同重金属离子也有不同的吸附容量蒙脱石Cr3+>Cu2+>Zn2+>Cd2+>Pb2+;高岭石Cr3+>Pb2+>Zn2+>Cu2+>Cd2+;伊利石Cr3+>Zn2+>Cd2+>Cu2+>Pb2+.     

Characteristics and distribution of clay minerals and their effects on reservoir quality: Huagang Formation in the Xihu Sag,East China Sea Basin

Abstract

The characteristics and distribution of clay minerals and their effects on reservoir quality in the Huagang sandstones in the Xihu Sag, East China Sea Basin were studied by using X-ray diffraction, casting thin-sections, scanning electron microscopy, electron microprobe analysis, fluid inclusion analysis, constant-rate mercury injection and nuclear magnetic resonance. Clay minerals consist of kaolinite, chlorite, illite and illite–smectite mixed layer (I/S); kaolinite forms from dissolved feldspars, chlorite occurs as clay coatings that are transformed from clay precursors owing to the flocculation of suspended detrital clays or the crystallisation of pore fluids, and illite forms from the illitisation of detrital smectite, authigenic kaolinite and K-feldspars. Clay distribution is controlled by sedimentary environments, burial history and lithologies. Typical reservoirs in the western sub-sag are thin and developed in braided river facies at relatively shallow burial depths with clays dominated by kaolinite. However, typical reservoirs in the central inversion tectonic zone are thicker and developed in a braided delta front facies at deeper burial depths with clays mainly consisting of chlorite, illite and I/S. High-quality reservoirs are characterised by coarse granularity, high quartz content and low clay content with widespread development of chlorite coatings that inhibit quartz cements at low temperatures. At higher temperatures, the high-quality reservoirs develop more pores providing growth space for quartz cements and result in the coexistence of chlorite coatings and quartz cements. The high-quality reservoirs are controlled by their lithological characteristics rather than chlorite coatings. Illite and I/S clays create severe damage to reservoirs by reducing the size and connectivity of pore-throats.     

Quantitative analysis of clay minerals and their admixtures

Clay minerals are of non uniform composition and particle size. Also their identification and nomenclature have given much confusion. Examples are given. Quantitative analysis of clay minerals from deposits and soils, by X-ray, thermo- and infrared analysis is treated. Examples are given of the large variability in the results; even for X-ray and electron microscope pure- and 85 to 90% chemical pure samples of kaolinite a well defined clay mineral. They are caused mainly by varying conditions of crystal growth from which result differences in isomorphous replacements, structure, ordering and strain. An amorphous weathering substance coating the mineral particles (Beilby layer) upsets in particular quantitative analyses of the finer kinds of clay minerals. Clay minerals from soils have, as compared to those from pure deposits, in particular formed by hydrothermal action, only poor characteristics of small intensity. Examples are given. Quantitative analyses are further hindered by specific characteristics for a certain mineral being masked by those of other minerals which usually occur in the same sample. Examples are given.     

江西赣南风化淋滤型稀土矿床中的粘土矿物研究

对江西赣南6个地区风化淋滤型稀土矿中全风化层的粘土矿物进行了研究,为进一步了解粘土矿物对该类型稀土矿中稀土元素分异的影响奠定了基础。X射线衍射自然定向片、甲酰胺片、饱和乙二醇片和加热片、红外光谱及扫描电镜观察结果表明该区粘土矿物以片状高岭石和针管状7埃洛石为主,其中坳背塘、长坑屋、上堡、杨村样品主体为高岭石,足洞样品中发育大量埃洛石,而石排样品中高岭石与埃洛石比例相当。电感耦合等离子体质谱分析表明稀土元素在粘土矿物中大量富集,其稀土元素配分不仅受到原岩的影响,而且受到粘土矿物本身性质的影响。Ce元素在足洞和石排样品的粘土矿物中表现出正异常,而在其他样品粘土矿物中表现为负异常,可能与其中发育的埃洛石密切相关。Ce元素可能以方铈矿胶膜的形式包裹在针状埃洛石中,和/或以离子形式被选择性吸附于埃洛石表面。     

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。     

吉林省中部黑土黏粒矿物的组成分析

为探讨玉米带黑土土壤退化的原因,通过X-射线衍射方法对吉林省中部玉米带黑土的黏粒矿物组成及分布进行了初步的研究,结果表明:黑土的黏粒矿物组成主要以2∶1型的蒙脱石及伊利石为主,二者总和达90%。伊利石在表层有增加的趋势,而蒙脱石向下则有增加的现象,此结果与黏粒的全量分析相一致。