颗石藻元素地球化学研究进展

颗石藻元素地球化学研究在古海洋学研究中有着重要意义。目前开始研究的主要有Sr/Ca和Mg/Ca比值。研究发现,颗石的Sr/Ca比值主要受颗石藻生长和钙化速度控制,其次受温度影响;而Mg/Ca比值主要与温度有关,属种间受影响程度有差别。样品清洗和单种分离是颗石藻元素地球化学分析的重点和难点。倒置显微镜挑出单种颗石是目前最为方便且准确的分析方法。颗石Sr/Ca比值可以用来反映古生产力,Mg/Ca比值可以用来重建古温度。     

生物壳体Sr／Ca、Mg／Ca、^87Sr／^86Sr比值在恢复古气候、古环境中的应用—以小渡口剖面为例

生物壳体的Sr/Ca、Mg/Ca比值能反映其沉积水体的Sr/Ca、Mg/Ca比值，在一定条件下反映水体的盐度、温度，并分别与宿生水体的盐度、温度呈正比关系。生物壳体的^87Sr/^86Sr比值是恢复盆地古水文条件的一种重要手段。本文以著名的泥河湾盆地小渡口剖面的第28层为实例，力图通过对有孔虫、介形虫、腹足类生物壳体Sr/Ca、Mg/Ca比值与^87Sr/^86Sr比值的对比研究，并结合前人所作的中更新世古地理特征研究，来恢复生物壳体沉积时泥河古湖水的温度、盐度，进而进行古气候、古环境的恢复。研究结果表明：在0.97-0.94Ma间，古泥河湾湖为一陆相湖泊，湖水的温度、盐度变化趋势相吻合，均呈低－高－低的演化特征，可能对应着盆地水体的扩展－退缩－扩展变化。其中，在0.96-0.95Ma间，古泥河湾湖具有较高的温度、盐度特征。     

滇东磷矿床中粘土矿物的研究

滇东磷矿床中粘土矿物分布比较广泛,在震旦系到寒武系各地层中均有分布。本文仅讨论下寒武统渔户村组中谊村段磷矿层夹层及顶、底板页岩中的粘土矿物。经化学分析、X射线衍射、红外吸收光谱分析、差热分析及电子显微镜分析,确定长区磷矿床中的粘土矿物主要是伊利石和伊利石/蒙脱石不规则混层矿物,其次为高岭石、变埃洛石,含少量海绿石。通过对混层矿物的研究,为本区矿物间的转化、沉积环境及成岩作用的探讨提供了重要的资料。     

天津蓟县长城系串岭沟组混层粘土矿物

为了解天津蓟县长城系串岭沟组地层中混层粘土矿物的组成和结构特征, 利用X射线粉晶衍射(XRD) 和高分辨透射电镜(HRTEM) 对其进行了深入研究.通过对比该区粘土矿物的自然干燥片、Ca离子饱和片、Ca饱和的乙二醇膨胀片、加热到375℃和550℃的乙二醇膨胀片获取的XRD衍射峰, 确定该区混层粘土矿物为伊利石/蒙脱石(I/S) 不规则混层矿物和绿泥石/蒙脱石(Chl/S) 不规则混层矿物.从高分辨透射电镜观察到I/S规则及不规则混层的晶格条纹像以及Chl/S不规则混层的晶格条纹像, 揭示了该区I/S混层和Chl/S混层的层间堆跺结构特征.该研究为蓟县中元古界典型剖面提供了重要的混层粘土矿物的结构信息.      

川东华蓥山二叠系／三叠系界线附近粘土层中粘土矿物的类型及成因

对川东华蓥山二叠系／三叠系界线附近粘土层中的粘土矿物进行野外采样和室内X射线衍射分析,结果表明,这些粘土矿物主要由规则混层伊利石-蒙脱石组成,其中1个样品可能舍有少量不规则混层绿泥石-蒙脱石等粘土矿物。总地看来．该界线粘土层中的规则混层伊利石-蒙脱石中伊利石层的含量自下而上呈现减少的趋势,平均含量约83％,所经历的最大古地温在125-150℃之间。这些粘土矿物的构成和特征与前人在华南其他地区相同层位取得的成果总体上具有较好的一致性．显示了该粘土层成因的相同性及所具有的等时意义。不同地区粘土矿物构成的差异性（如高岭石的存在与含量）可能与二叠系／三叠系界线不整合的存在与否或间断时间有关,规则混层伊利石-蒙脱石的混层比则与埋藏历史和沉积-沉积期后的流体介质有关。     

川东华蓥山二叠系/三叠系界线附近粘土层中 粘土矿物的类型及成因

对川东华蓥山二叠系／三叠系界线附近粘土层中的粘土矿物进行野外采样和室内X射线衍射分析,结果表明,这些粘土矿物主要由规则混层伊利石-蒙脱石组成,其中1个样品可能舍有少量不规则混层绿泥石-蒙脱石等粘土矿物。总地看来．该界线粘土层中的规则混层伊利石-蒙脱石中伊利石层的含量自下而上呈现减少的趋势,平均含量约83％,所经历的最大古地温在125-150℃之间。这些粘土矿物的构成和特征与前人在华南其他地区相同层位取得的成果总体上具有较好的一致性．显示了该粘土层成因的相同性及所具有的等时意义。不同地区粘土矿物构成的差异性（如高岭石的存在与含量）可能与二叠系／三叠系界线不整合的存在与否或间断时间有关,规则混层伊利石-蒙脱石的混层比则与埋藏历史和沉积-沉积期后的流体介质有关。     

巴音戈壁盆地巴音戈壁组上段古盐度恢复及意义

巴音戈壁盆地巴音戈壁组上段泥岩是中国高放废物深地质处置的目标研究层位之一,目前缺乏对该地层湖相泥岩粘土矿物组合特征及古盐度影响因素的相关认识。文章应用全岩的B含量、Sr/Ba比值、Rb/K比值及Na+K质量分数等方法和X衍射测试分析技术对巴音戈壁组上段古盐度进行综合判别。分析得出：（1）巴音戈壁组上段以半深湖—深湖沉积环境为主,发育有厚层深灰色泥岩,以半深湖至深湖相沉积为主;（2）研究区目的层岩性结构为泥粉质,该段泥岩伊利石、蒙脱石、伊蒙混层发育较好,绿泥石和高岭石极少;（3）选取样品的Sr/Ba、Rb/K、B/Ga、Na+K值同Couch公式恢复的古盐度变化趋向相似,其水体以半咸水、微咸为主;（4）随着深度增加,TZK-1井、TZK-2井的古盐度呈规律变化,具有升高—降低特点,与伊利石含量的变化一致,并且古盐度变化与古气候及氧化还原的相关研究在该岩性段位耦合。综上表明：目标区古盐度的研究不仅有利于湖盆古沉积环境的恢复,而且有助于揭示古盐度的变化特征对粘土矿物组合特征及演化的影响,为后期深入研究粘土矿物对核素吸附性能及核素在泥岩中的迁移情况提供一定依据。     

云南思茅盆地勐野井组碎屑岩矿物学、地球化学特征及古盐湖沉积环境演化

通过对云南思茅盆地勐野井钾盐矿区钻孔岩心的碎屑沉积物进行粘土矿物分析和元素地球化学分析探讨了研究区晚白垩世碎屑岩的物源属性及古盐湖沉积环境演化特征。粘土矿物组合特征及La/Th-Hf、La/Sc-Th/Co、La-Th-Sc图解,Cr/Th、Al2O3/TiO2比值等表明该孔碎屑岩的物源主要为长英质花岗闪长岩。主量元素活动性分析表明化学风化过程中随着粘土矿物的形成首先发生Ca和Na的淋失,K、Mg则在这一过程中呈富集态势,而Fe、Mn主要受物源限制而总体上表现为亏损。结合粘土矿物形成条件,认为研究区古盐湖经历了暖湿—暖干(成盐成钾期)—暖湿(淡化)的古气候转化过程。而粘土矿物组合受高盐极端环境与埋藏成岩作用影响显著,表现为成盐成钾期显著的伊利石化和绿泥石化作用。因此伊利石+绿泥石粘土矿物组合,结合富Mg绿泥石的相对含量,以及相应沉积阶段碎屑岩的MgO异常高值,可有效指示古盐湖成盐成钾的演化阶段。!     

土壤菌与蒙脱石相互作用特性研究

为了探讨土壤菌与蒙脱石相互作用体系的特性,本文选取了11株吸附Sr2+效果较好的土壤菌株与提纯好的蒙脱石进行相互作用。通过对土壤菌与蒙脱石相互作用1d后培养液的pH值、葡萄糖(GLU)、Ca2+、Mg2+、Na+等的变化测试,比较了土壤菌株与蒙脱石作用后的特性变化;利用XRD分析,对土壤菌作用后的蒙脱石层间距变化进行了初步研究。结果表明吸附Sr2+效果较好的菌株大多数消耗GLU,阴性菌占大多数;与蒙脱石作用1 d后,GLU消耗率提高。与蒙脱石作用后,溶液pH有所上升。离子溶出比例趋势:Ca2+>Mg2+>Na+。蒙脱石与土壤菌相互作用1d后,层间距都有所增大,层间距的扩增与GLU消耗呈现一定的关系。与革兰氏阴性菌相比较,革兰氏阳性菌与蒙脱石相互作用1d后,蒙脱石层间距的扩增较大。     

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。     

巴州坳陷下白垩统—中侏罗统的粘土矿物特征

根据岩石薄片、Ｘ衍射和扫描电镜分析资料,本文研究了巴州坳陷下白垩统—中侏罗统粘土矿物特征,发现粘土矿物分为伊利石、伊／蒙混层和绿泥石三种类型。粘土矿物的类型和含量随深度而变化,形成了伊／蒙混层带、混层迅速转化带和伊利石带。粘土矿物的转化和自生粘土矿物的形成是沉积地层非常重要的成岩变化。     

Rock composition and origin of the Duwi Formation calcareous rocks, Upper Egypt

Upper Cretaceous phosphorite beds of the Duwi Formation, Upper Egypt, are intercalated with limestone, sandy limestone, marl, calcareous shales, and calcareous sandstone. Calcareous intercalations were subjected to field and detailed petrographic, mineralogical and geochemical investigations in order to constrain their rock composition and origin. Mineralogically, dolomite, calcite, quartz, francolite and feldspars are the non-clay minerals. Smectite, kaolinite and illite represent the clay minerals. Major and trace elements can be classified as the detrital and carbonate fractions based on their sources. The detrital fraction includes the elements that are derived from detrital sources, mainly clay minerals and quartz, such as Si, Al, Fe, Ti, K, Ba, V, Ni, Co, Cr, Zn, Cu, Zr, and Mo. The carbonate fraction includes the elements that are derived from carbonates, maily calcite and dolomite, such as Ca, Mg and Sr. Dolomite occurs as being dense, uniform, mosaic, very fine-to-fine, non-ferroan, and non-stoichiometrical, suggesting its early diagenetic formation in a near-shore oxidizing shallow marine environment. The close association and positive correlation between dolomite and smectite indicates the role of clay minerals in the formation of dolomite as a source of Mg^2＋ -rich solutions. Calcareous rocks were deposited in marine, oxidizing and weakly alkaline conditions, marking a semi-arid climatic period. The calcareous/argillaceous alternations are due to oscillations in clay/carbonate ratio.     

Illite mineral synthesis at surface temperatures

The synthesis of illite mixed-layer minerals at surface conditions is possible through precipitation of Al hydroxides from Si-, Mg- and K-containing solutions. It has been shown that amorphous hydroxides of Al, Fe, etc. are capable of coprecipitating silica even from very dilute solutions. By aging of these X-ray amorphous hydroxide—silica precipitates under certain conditions, clay minerals can be synthesized at low temperatures. The presence of Mg particularly favors the formation of three-layer clay minerals. Mg-rich Al hydroxide—silica precipitates permit formation of tri- and di-octahedral smectite, illite and chlorite. The formation of three-layer clay minerals is only possible when the precipitates contain at least 6% MgO. The precipitates stay amorphous if the Mg content is lower. The adsorption of Mg and K on the hydroxide—silica precipitate controls the illite or montmorillonite portion in the mixture of the three-layer silicates. There is a competition for K and Mg adsorption on the hydroxide—silica precipitates. Higher K concentration inhibits the three-layer mineral formation through the lowering of the Mg content in the precipitates. Illite mineral formation is favored under certain K/Mg ratios. Higher NaCl contents do not favor the three-layer mineral formation.The enrichment of Mg and K in the precipitates is not as large as the enrichment of Si in the hydroxides. This means that the illite mineral formation is only possible from solutions with a high-salt content like seawater.     

Barium partitioning in coccoliths of Emiliania huxleyi

The coccolithophore Emiliania huxleyi was grown in seawater under different Ba concentrations. The relationship of coccolith Ba/Ca ratio and seawater Ba/Ca ratio was found to be linear. The linear regression yields the apparent Ba exchange coefficient of 0.10. Our data support a recently proposed generic model (Langer G., Gussone N., Nehrke G., Riebesell U., Eisenhauer A., Kuhnert H., Rost B., Trimborn S., and Thoms S. (2006) Coccolith strontium to calcium ratios in Emiliania huxleyi: the dependence on seawater strontium and calcium concentrations. Limnol. Oceanogr.51, 310-320.) developed for explaining apparent exchange coefficients of metabolically inert divalent trace metals, such as Sr, in E. huxleyi. This model represents the first approach combining cell physiological processes and data from inorganic precipitation experiments, which quantitatively explains coccolith apparent Sr and Ba exchange coefficients.     

Factors affecting the association of fatty acids with mineral particles in sea water

Certain factors influencing the incorporation, transport and release of fatty acids by clay minerals, calcite and marine sediments have been investigated.Salinity was found to be an important factor. The adsorption of heptadecanoic acid by bentonite clay at 4%. was nearly triple that at 0%.. However, from 4%. to 35%., only a minor adsorption increase occurred. This behavior is believed to be related to flocculation of the clay at the lower salinity range. The pH over the range of 6.0–8.5 has a small influence on fatty acid-clay association, depressing it somewhat as the basicity increases.When the temperature of the fatty acid solution was increased from 0°C to 50°C, a decrease in adsorption on to clay was found. This effect may be due to increased water solubility of the acid at higher temperatures, since solubility is very important in controlling the degree of fatty acid-mineral interaction. Furthermore, apparent solubilization of fatty acids by indigenous dissolved organic matter in sea water reduces adsorption on to clay minerals.Based upon the heat of adsorption of ?14.6 kcal/mole, fatty acids are physically bound to clay minerals by weak van der Waals forces and hydrogen bonds.Bentonite and kaolinite were found to be the most adsorptive minerals investigated, followed in order by illite, montmorillonite and calcite. Sediments from Narragansett Bay were found to lie between illite and montmorillonite in adsorptive capacity after indigenous sediment organic matter had been removed. Sediment organic matter reduced fatty acid uptake by a factor of 1.6.     

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.     

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。     

蒙脱石+伊/蒙混层+伊利石等粘土矿物混合物相X射线定量分析方法—模拟定量法

本文提出粘土矿物(特别是含伊/蒙不规则混层粘土矿物)混合物相的X射线定量分析方法——模拟定量法。着重解决在蒙脱石-不规则伊/蒙混层粘土矿物-伊利石组合中,伊/蒙混层粘土矿物的定量分析计算。模拟定量法是对以前的各种粘土矿物X射线定量分析方法的补充。用纯净的蒙脱石、伊利石、高岭石、绿泥石及各种伊/蒙混层比的伊/蒙混层粘土矿物,配制了各种不同组合的粘土矿物混合样品,制成定向薄膜片,进行了X射线分析,讨论了各种组合的粘土矿物混合物相X射线衍射图谱的特征,并在此基础上提出了粘土混合物相定量分析的方法。