Study of the Stacking Sequences of an Irregular Mixed-Layer Illite/Smectite (I/S) Clay Mineral—with a Discussion on the Existence of Minerals with Two-Dimentional Lattice and One-Dimentional Quasi-Lattice

There are two aspects in the study of irregular mixed-layer clay minerals: one is the kinds and ratios of their basic structural unit layers and the other is the junction probabilities of the unit layers. Irregular mixed-layer illite/smectite clay minerals (I/S) are widespread in nature. While studying the clay minerals from the Permian-Triassic (P/T) boundary bed, the authors found that I/S clay minerals are developed in all P/T boundary clay layers in areas from the northwest to southeast of China. Systematic mineralogical studies of the I/S clay minerals from Hunan, Hubei, Sichuan and Zhejiang were made by means of X-ray, infrared spectroscopic, electron microscopic and chemical analyses and a deepened study of the stacking sequences of their structural unit layers was conducted by the MacEwan one—dimentional direct Fourier transform. It was found that the stacking of the illite and smectite crystal layers along the c axis can be derived from Fibonacci sequences. Hence, the authors propose that such I/S clay minerals are possessed of two—dimentional crystal lattice and one—dimentional quasicrystal lattice.

Illite-smectite Mixed-layer Minerals in the Alteration Volcanic Ashes under Submarine Environment

The clay mineralogy of the clay intervals interbedded with siliceous mudstones across the Permian-Triassic boundary (PTB) in Pengda, Guiyang, Guizhou province, was investigated by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The clay mineral assemblages of the sediments are mainly I/S clays and minor smectite, kaolinite, and illite as reveled by XRD analyses. The peak-shape parameters BB1 and BB2 of I/S clays of the representative clay bed PL-01 are 4.7° and 4.4°, and the peak position of the low angle reflection is at 6.8° 2θ (13.6 ), suggesting that the I/S clays has a IS type of ordering. However, the presence of multi-order reflections and their intensities are different from those of completely ordered 1∶1 mixed-layer I/S clay rectorite, indicating that I/S clays of the Pengda section have partially ordered IS structures. HRTEM observations show that most of the I/S clays exhibit an IS stacking ordering. However, in some areas within a IS particle, smectite layer is observed in doublets, triplets, and quartets, which are interstratified by various amounts of illite layers, suggesting the presence of other irregular stacking in addition to the major 1∶1 IS ordered stacking. Transformation of smectite layer into illite layers is also observed in the I/S clays, suggesting that the Pengda I/S clays are derived from smectite illitization, in good agreement with the clay mineral assemblage. The I/S clays of the Pengda section contain up to 45% to 95% smectite layer, the notably higher contents of smectite layer relative to those of other PTB stratigraphic sets in south China can be attributed to difference in alteration and smectite illitization processes due to different sedimentary environments.

Illite Crystallinity Mapping of Very Low Grade Metamorphism of Triassic Metapelites in the Zoigê Area,Western China

X-ray diffraction methods for estimating the metamorphic grade of diagenetic, anchizone and epizone in metapelites are reviewed and applied to samples from a 7000 m＋ borehole in western China and surface samples from the surrounding Zoige area. Kiibler＇s illite crystallinity （IC） measurements provide more consistent results than calculated values of percentage of illite in the I/S mixed layers and percentage of I/S mixed layers. Down-borehole IC values display a typical burial metamorphic relationship between stratigraphic level and IC. A method for preparing very low grade metamorphic maps is described, and isograds plotted on a regional geological map at selected values of IC, delineating a high temperature diagenetic zone, an anchizone, and an epizone. The map shows that IC values are controlled by stratigraphic level in the north of the study area （i.e. burial metamorphism）, and proximity to an igneous intrusive body in the south （i.e. contact metamorphism）.

鄂尔多斯盆地中-上元古界—下古生界热演化程度:来自伊利石结晶度及伊蒙混层的指示

由于缺乏有效的古温标,对鄂尔多斯盆地中-上元古界—下古生界热演化程度一直以来了解十分有限。本文通过对盆地内20余口钻井中-上元古界—下古生界开展自生伊利石结晶度和伊蒙混层系统性测试,试图从新的角度分析盆地中-上元古界—奥陶系热演化程度及分布规律。结果表明:盆地不同部位伊利石结晶度与深度关系存在明显的差异,整体具有随深度增大而减小的趋势,主要受控于古埋深及古地温梯度。盆地沉积盖层伊利石结晶度普遍大于0.25,未达到绿片岩相浅变质阶段;盆地下古生界奥陶系伊利石结晶度大于0.42,表明处于成岩演化阶段;寒武系样品结晶度略小于奥陶系,整体处于成岩带中-晚期到极低级变质作用阶段;中元古界伊利石结晶度相对更低,对应热演化程度更高。此外,我们对比了伊利石结晶度和等效镜质体反射率分别恢复的地层最大古地温结果,两者在误差范围内基本一致,表明这一方法对研究我国古老地层热演化程度具有明显的可行性。

Evolution of kaolinite subgroup minerals and mixed-layer illite/smectite in the Paleogene Damintun Depression in Liaohe Basin of China and its implication for paleotemperature

The oil-rich Damintun Depression is located in the Liaohe Basin, Northeast China, and was formed during the Paleogene. The major oil-producing strata in the depression are mudstone and shale. To explore the burial diagenetic history of the basin and the formation thresholds of hydrocarbons, the characters of the kaolinite subgroup minerals and mixed-layer illite/smectite in the mudstone and the shale are studied by using X-ray diffraction, electron probe, scanning electron microscope, and Fourier infrared spectrum. The kaolinite subgroup consists of kaolinite and halloysite. The kaolinite is flake-like or vermiform-like. The halloysite is in long tubular shape and its length is related to its iron content. A longer tube has lower iron content. The crystallinity of kaolinite is 0.40 ~20, and its degree of order increases from 0.03 to 1.17 with the burial depth. Kaolinite is in disorder when the buried depth is less than or equal to 2479 m, and it is partially ordered when the buried depth is greater than 2479 m. Kaolinite is supposed to turn into dickite when the depth is greater than 2550 m, but low penetrability and low poros- ity of the shale and mudstone prevent such a change. The mixed-layer illite/smectite changes from disorder to order continually as the buried depth increases. Its disorder （RoI/S）, as defined by illite layer content （I%）, is smaller than 50% at depths less than 2550.25 m. Based on Hoffman ＆ Hower＇s model, the paleo-geothermal gradients of 3.37-3.76℃/100 m （3.57℃/100 m on average） can be derived in the Paleocene Damintun Depression, which is significantly higher than the present geothermal gradient （2.9℃00 m）. The threshold depth of the oil formation in the depression is about 2550 m.

From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water

A series of mesoporous silicate adsorbents with superior adsorption performance for hazardous chlortetracycline（CTC） were sucessfully prepared via a facile one-pot hydrothermal reaction using low-cost illite/smectite（IS） clay,sodium silicate and magnesium sulfate as the starting materials.In this process,IS clay was ＂teared up＂ and then ＂rebuilt＂ as new porous silicate adsorbent with high specific surface area of 363.52 m^2/g（about 8.7 folds higher than that of IS clay） and very negative Zeta potential（- 34.5 mV）.The inert Si- O- Si（Mg,Al） bonds in crystal framework of IS were broken to form Si（Al）- O^- groups with good adsorption activity,which greatly increased the adsorption sites served for holding much CTC molecules.Systematic evaluation on adsorption properties reveals the optimal silicate adsorbent can adsorb 408.81 mg/g of CTC（only 159.7 mg/g for raw IS clay） and remove 99.3%（only 46.5%for raw IS clay） of CTC from 100 mg/L initial solution（pH 3.51;adsorption temperature 30℃;adsorbent dosage,3 g/L）.The adsorption behaviors of CTC onto the adsorbent follows the Langmuir isotherm model,Temkin equation and pseudo second-order kinetic model.The mesopore adsorption,electrostatic attraction and chemical association mainly contribute to the enhanced adsorption properties.As a whole,the high-efficient silicate adsorbent could be candidates to remove CTC from the wastewater with high amounts of CTC.

Occurrence of mixed-layer illite/smectite at temperature of 285℃ in an active hydrothermal system and its significance

THE progressive transformation of smectite into illite via mixed-layer illite/smectite (I/S) phases occurs during hydrothermal alteration, burial diagenesis and regional metamorphism. The proportion of illite or smectite (also indicated by their expandability) and ordering of I/S, interpreted by X-ray powder diffraction (XRD) profiles, have long been used as geothermometers in sedimentary basins. It is found that R=1 ordering mixed-layer I/S still exists

Kinetic model for the smectite to illite transformation in active geothermal systems

The smectite to illite transformation in active geothermal systems of New Zealand can be simulated by a first_order reaction kinetic model, which provides direct estimates about the minumum ages of active geothermal systems themselves. The derived kinetic values show that the smectite to illite transformation is sensitive to both temperature and time.

纳米伊/蒙粘土对铅和镉污染土壤钝化效果研究

本文选取矿区周边铅和镉复合重金属污染的农田土壤,添加纳米伊/蒙粘土,进行了农田铅和镉钝化试验,评价纳米伊/蒙粘土降低溶液铅和镉浓度以及降低土壤铅和镉有效态含量的效果。结果表明,纳米伊/蒙粘土对溶液铅和镉离子吸附过程遵守Langmuir等温模型,其饱和吸附量分别是263.16mg·kg^(-1)和13.32 mg·kg^(-1)。与对照相比,添加1%纳米伊/蒙粘土,醋酸提取的土壤铅和镉有效态浓度分别下降了34.07%和34.04%;196天后分别下降23.74%和45.86%,说明纳米伊/蒙粘土能一定程度降低土壤铅和镉有效态浓度,形态分析表明纳米伊/蒙粘土可同时促进土壤铅和镉从不稳定态向稳定态转化。

贵州大方不规则I/S间层粘土的矿物学特征

本文叙述了贵州大方伊 /蒙不规则间层粘土 (I/S)的矿物学特征 ,包括矿物组成、化学成分、谱学特征、显微形貌特征以及理化特征 ,并对其应用前景进行了探讨。结合XRD和HRTEM两方面证据 ,获得了关于该矿物在C轴方向上的堆垛方式 ,三种以上共存的间层作用类型有力地证实了其不规则性。

伊蒙混层粘土I/S比加大方式及成分控制──以珠江口盆地两口井为例

对珠江口盆地两口井泥质岩中粘土矿物Ｘ衍射分析资料的分段定量研究证实，在渐进成岩过程中，伊蒙混层粘土的伊利石层和蒙皂石层的含量之比（Ｉ／Ｓ）的加大，与钾长石的溶解有关。有三种形式：若沉积有机质和钾长石足够丰富，加大将优先以伊利石层净增加的方式进行，其出现的温度大致与生油门限温度相当或稍高；低于该温度，蒙皂石层将按溶解沉淀机理伊利石化；若无Ｋ＋供给，加大方式将是蒙皂石净溶解。一般情况下的渗透率均可保证离子的通畅输导而与加大方式无关；仅当渗透率低到只对较大的铝的有机络合离子具有过滤作用时，才可能使净增伊利石层被伊利石化反应所取代；更低渗透率或体系封闭将使所有加大行为趋于停止。

Diversified roles of mineral transformation in controlling hydrocarbon generation process,mechanism,and pattern

Organic matter(OM)is intimately associated with minerals in clay-rich mudstones,leading to widespread organic-mineral interaction during hydrocarbon generation in argillaceous source rocks.What we are concerned is the effects of the different mineral properties on hydrocarbon generation process and mechanism during mineral transformation.In this way,pyrolysis experiments with smectite-octadecanoic acid complexes(Sm-OA and Ex-Sm-OA)were conducted to analyze correlation of mineralogy and pyrolysis behaviors.Based on organicmineral interaction,hydrocarbon generation process was divided into three phases.At 200–300℃,collapse of smectite led to desorption of OM,resulting in high yield of resin and slight increase in saturates.Subsequently,enhanced smectite illitization at 350–450℃was accompanied with large amounts of saturates and a mere gaseous hydrocarbon.Featured by neoformed plagioclase,ankerite,and illite,500C saw plenty of asphaltene and methane-rich gaseous hydrocarbons,revealing cracking reactions of OM.Noteworthy is that saturated and gaseous hydrocarbons in Ex-Sm-OA were considerably more than that in Sm-OA during second and third phases.Quantitative calculation of hydrogen revealed organic hydrogen provided by cross-linking of OM could not balance hydrogen consumed by cracking reactions,but supply of inorganic hydrogen ensured cracking could readily occur and consequently greatly promoted hydrocarbon generation.Further investigating characteristics of mineralogy and pyrolytic products,as well as effects of solid acidity on hydrocarbon generation,we concluded desorption of OM and decarboxylation promoted by Lewis acid were dominated at 200–300C,resulting in lowdegree hydrocarbon generation.While high yield of saturated and gaseous hydrocarbons in second and third phases,together with occurrence of ankerite,indicated predominance of decarboxylation and hydrogenation promoted by Lewis and Brønsted acid,respectively.Variations in organic-mineral interactions indicated(1)the controls of mineral transformation on hydrocarbon generation process and mechanism include desorption,decarboxylation,and hydrogenation reactions;(2)clay minerals acted as reactants evolving together with OM rather than catalysts.These findings are profoundly significant for understanding the hydrocarbon generation mechanisms,organic-inorganic interactions,and carbon cycle.

About retardation of a physicochemical processes in overpressured sediments, South-Caspian basin, Azerbaijan

In paper the role of excess pressures in cata- genic processes of the South-Caspian basin (SCB) is considered. The results of the carried out researches taking into account world ex- perience on the given problem allow to con- clude, that SCB (mainly its deep-water part), as well as a number of other basins of the world with overpressures, is characterized by retarda- tion of processes cracking of kerogen and oil, and also reaction of transformation of clay minerals. Periodic intensification of these pro- cesses can provoke development of diapirs and mud volcanoes, which are the centers of pulse unloading of a hydrocarbon products from sys- tem. The conclusion about high prospects of revealing of hydrocarbon accumulations in deep buried deposits in overpressured basins is made.

Characterization of Soil Clay Minerals of the River Nile Sediments, Sohag Region, Egypt： Decomposition of X-Ray Diffraction Patterns

Up till now all the clay mineral studies on the soils of the River Nile flood plain in Egypt could not trace the very rapid mineral change observed in these soils. So, the clay mineralogy of the River Nile flood plain soils in Sohag region, Egypt, has been studied using the method of numerical analysis of X-ray diffraction recordings （curve decomposition） as a new, powerful tool for precise mineral identification. The X-ray patterns of the studied soil clay fraction show that 2：1 clay minerals are much more abundant than kaolinite and that this clay fraction contains fair amounts of K-feldspar and quartz. XRD pattems obtained on the 〈 2 μm fraction of the River Nile sediments indicate the presence of smectite, mixed-layer illite-expanding minerals, kaolinite, mica-illite and chlorite. The decomposed XRD patterns reveal significant changes in the mineralogy of the clays. The major clay phases present in the 4-11 20 range are well crystallized illite （10 A）, poorly crystallized illite （10.2-10.4 A）, two mixed-layer I-S （illite/smectite） minerals, one with a peak near 13.5 A （rich-smectite） and the other near 11 A （rich-illite）.

山东昌潍古近系原型盆地粘土矿物的成岩演化与古地温

山东昌潍盆地形成于古近系的古新世-始新世早期(Ek-Es_4),本文主要研究昌潍盆地的粘土矿物特征及其古地温。昌雄古近系(Ek-Es_4)原型盆地的粘土矿物种类有:无序高岭石、伊/蒙混层矿物、伊利石和辉绿泥石(铁斜绿泥石)。利用粘土矿物温度计估算了盆地埋藏深度的古地温,探讨了古近系(Ek-Es_4)原型盆地的成岩作用和有机质热演化阶段。研究表明:随着埋藏深度的增加,伊/蒙混层矿物(L/S)由无序向有序连续转变;高岭石的有序性、伊利石和绿泥石的结晶程度趋于增强。根据伊/蒙混层矿物(L/S)地温计获得盆地不同深度的成岩温度范围;成油深度约为3000～4000m±。现今地温与古地温的对比,显示盆地存在热异常,导致热异常的形成可能有以下几方面因素:(1)盆地曾经历过地壳抬升阶段;(2)盆地内有岩浆活动热事件发生;(3)盆地裂陷期的构造动力学作用导致古地温梯度过高。昌潍原型盆地较高的古地温梯度吻合于裂陷盆地构造动力学演化的模式。

蒙皂石粘土矿物不正常转化的研究——以准噶尔盆地为例

利用岩石薄片和X射线衍射资料,分析了准噶尔盆地腹部地区蒙皂石粘土矿物的不正常转化。该区庄1井、成1井和董1井在超压段内粘土矿物转化出现异常现象,蒙皂石以及伊/蒙混层的相对含量随深度增加有所增加,而伊利石的相对含量随深度增加有所减少。结合前人的研究资料,讨论了超压对粘土矿物转化的影响。超压能增加蒙皂石层间水的稳定性,阻碍超压仓与外界流体和离子的交换,使伊利石含量有所减少。同时,火山岩屑物质的大量存在可能导致在晚成岩阶段伊/蒙混层含量较高,蒙皂石的含量也有所增加。

合肥盆地东部朱巷组X射线衍射分析及其油气意义

对取自合肥盆地大桥凹陷内下白垩统朱巷组(K1Z)21个泥岩样粘土矿物进行X射线衍射分析,定量研究表明,伊利石结晶度值均大于0.42,一般为0.42～0.75。伊利石/蒙皂石混层比有5个样品小于50.00%,其余为50.20%～70.10%,蒙皂石转化从无序间层到部分有序间层,反映地表处朱巷组处于成岩作用中-早期阶段,有机质成熟度处于成熟-未成熟阶段,没有进入埋藏变质。结合钻井Ro资料及地球物理资料,揭示朱巷组埋深大于3000m,预测深埋地下的朱巷组烃源岩已进入生油门限。

纳米伊／蒙黏土对水体中重金属的吸附去除效果

为明确纳米伊/蒙黏土(下称伊/蒙黏土)作为修复材料在去除水体重金属方面的应用潜力,研究了伊/蒙黏土对水体中Ni^(2+)、Cu^(2+)和Cd^(2+)的去除效果与吸附规律,并通过小麦水培试验分析伊/蒙黏土降低水体重金属在小麦地上部分的累积和缓解重金属对小麦的毒害效应等效果.结果表明:伊/蒙黏土可以吸附去除水体中的Ni^(2+)、Cu^(2+)和Cd^(2+),当水体中ρ(Ni^(2+))、ρ(Cu^(2+))和ρ(Cd^(2+))分别为5、10、2 mg/L时,添加2%(以w计)的伊/蒙黏土对3种重金属的去除率均达到95%以上.伊/蒙黏土对重金属的吸附等温线符合Langmuir方程,对Ni^(2+)、Cu^(2+)和Cd^(2+)的理论最大吸附量分别为2.13、8.52和1.56 mg/g.在培养液中添加2%伊/蒙黏土可降低小麦对Ni^(2+)、Cu^(2+)和Cd^(2+)的累积富集,缓解重金属对小麦生长的毒害效应.研究显示,纳米伊/蒙黏土可有效去除水体中的Ni^(2+)、Cu^(2+)和Cd^(2+),并缓解其对小麦的毒性,因此其在修复水体重金属污染、恢复水环境生态功能方面具有潜在的应用前景.

油气储层中自生伊利石K-Ar同位素年代学研究若干问题的初步探讨

对油气储层中自生伊利石K Ar体系产生影响的有关问题如砂岩岩性、伊利石 /蒙皂石间层矿物的间层比和绿泥石进行了初步试验和讨论。结果表明 :中、细砂岩的应用效果相对较好 ,粉砂岩、泥质粉砂岩则难度较大 ;I/S有序间层的应用效果相对较好 ,I/S无序间层则难度较大 ;绿泥石对自生伊利石K Ar体系测年结果的影响不明显。油气注入可能是引起伊利石成岩作用终止的原因之一。最后对各种典型年龄剖面可能的成因解释进行了简要介绍和初步探讨。

不规则伊/蒙混层粘土矿物成因类型及晶体化学分类

不规则伊/蒙混层粘土矿物(I/S)分布极为广泛,根据大量资料,提出了I/S的成因及晶体化学分类。按其成因分为三类:成岩型、风化型、火山热液型;按其晶体化学性质分为完全无序型、部分有序型及准晶态型。讨论了各成因类型I/S的晶体化学特点,认为产出于P/T界线层粘土中的I/S具二维晶格一维准晶格。探讨了I/S与烃类形成的关系。