蒙皂石—伊利石演化及有关问题的理论探讨

摘要：作者认为蒙皂石—伊利石的转化是多因素、多机制作用的结果．不同环境、不同机制形成的伊／蒙混层矿物,有序化出现时的伊利石层含量不同。伊／蒙混层由无序到有序是一个连续的渐变过程,存在过渡型混层矿物,多数伊／蒙混层矿物都是以某一类型为主的复杂集合体。作者指出分散蒙皂石是影响无序型伊／蒙混层矿物混层比计算精度的主要因素。     

Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks,Bowen Basin,Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite–smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R≥3) illite–smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)_sn ratios show negative correlations with the illite content in illite–smectite and positive correlations with the δ¹⁸O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)_sn ratios and illite content in illite–smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/rock ratio conditions. Increasing HREE enrichment with δ¹⁸O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin.Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins.     

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.      

苏北盆地粘土矿物转化模式与古地温

以苏北盆地为例,系统研究了火成岩发育区粘土矿物组合特征及其控制因素;建立了粘土矿物转化模式;根据粘土矿物成岩演化特点,进行古地温分析。研究表明,苏北地区粘土矿物的分布主要受埋藏成岩作用、岩浆侵入、母质来源三种因素的影响,发育四种类型的粘土矿物组合和三种粘土矿物转化模式;火山碎屑岩母岩区和基性岩浆侵入区具有特殊的粘土矿物组合和成岩演化模式,前者以富含蒙皂石矿物为特点;后者出现高岭石与伊/蒙有序间层矿物共生组合,并具有不连续的演化序列;苏北盆地短有序I/S矿物出现于镜质组反射率 0.5 %～ 0.5 5 %的深度,伊/蒙间层矿物转变成伊利石在镜质组反射率 0.75 %～ 0.8%,可以用于热成熟度和古地温的估算;而蒙皂石消失的界面则不具有指标意义     

Study of the Stacking Sequences of an Irregular Mixed—Layer Illite / Smectite (I / S) Clay Mineral1

Abstract 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.     

沉积岩中自生伊利石K-Ar定年研究——存在问题及原因讨论

在浙江长兴煤山全球二叠系一三叠系界线层型剖面中界线附近采集黏土岩样品。对其中的伊利石／蒙皂石成岩间层I／S进行K—Ar测年实验研究，来探讨沉积岩中自生伊利石K—Ar测年在确定沉积地层时代方面的可行性。结果表明，沉积岩中成岩间层I／S的K—Ar年龄在没有碎屑含钾矿物混入的情况下，比其对应的地层时代要年轻，其原因主要有两条，一是因为泥岩中的自生伊利石来自于蒙皂石的伊利石化，而蒙皂石的伊利石化受很多因素控制，需要一定的时间才能完成；另一原因是由于蒙皂石伊利石化过程中存在着放射性成因^40Ar的扩散丢失。     

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.     

大方不规则伊／蒙间层矿物研究

通过X射线衍射、红外光谱、热分析、理化性能测试和镜下观察等手段,确定了贵州大方猫场含黄铁矿粘土岩中主要粘土矿物为伊/蒙不规则间层矿物,其间层作用类型为R=1,即累托石型有序间层。     

岩浆母质对蚀变粘土矿物的约束:以贵州新民剖面P-T界线附近火山灰层为例

目前对于粘土层中伊蒙混层矿物的堆垛结构、单元层含量与岩浆母质及环境条件关系的了解等,仍然十分匮乏.一定沉积环境下火山灰层中粘土矿物组合、以及伊蒙混层堆垛方式精细结构特征,可能记录了沉积(包括成岩作用) 环境对火山物质蚀变产物的影响.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、元素地球化学分析、氧同位素分析方法等方法,对贵州新民深海相二叠系-三叠系(P-T) 界线附近蚀变火山灰层的地球化学特征、粘土矿物精细结构特征等进行了深入研究.结果表明,4个火山灰粘土层均含有2种具有R3结构、不同混层比的伊蒙混层矿物相,且均出现粘土矿物集合体取代原先的火山碎屑颗粒或在颗粒表面生长的现象,粘土矿物形成于沉积-成岩阶段因而其泥质结构被保留;样品XM-5-1和XM-5-2的Fe3+原子数分别为0.16和0.17个且具有明显Eu负异常和较低的K₂O含量,而XM-5-3和XM-5-4的Fe3+原子数均为0.14个,说明相对于前2个粘土层,后2个的岩浆母质更加偏向酸性而表现为成岩蚀变程度更强.粘土矿物的氧同位素组成为17.3‰~18.1‰,与常温下蒙脱石与海水的平衡数值相近,表明粘土矿物化学组成与海底成岩蚀变环境有关,而不同火山灰层的粘土矿物学特征则主要取决于岩浆岩母质以及成岩蚀变强度.      

Clay record of climate change since the mid‐Pleistocene in Jiujiang,south China

To obtain a better understanding of climate change in south China in the Quaternary, a clay mineralogical study was undertaken on the red earth profile at Jiujiang, using X‐ray diffraction (XRD) and particle‐size distribution analysis methods. The XRD results showed that the clay minerals of the Jiujiang red earth were mainly mixed‐layer illite–smectite (I/S), illite, kaolinite and vermiculite, with trace amounts of mixed‐layer kaolinite–smectite (K/S). Changes in clay mineral composition displayed a trend of three‐stage evolution. The higher mixed‐layer I/S clays and kaolinite contents in the lower portion suggest extremely warm and humid climates over the period c. 700 to c. 350 ka ago. A gradual decrease in I/S clays and kaolinite reveals a gradual climate change from warm/humid to cool/dry during the period c. 350 to c. 130 ka ago. The higher illite and vermiculite contents indicate a relatively cool and dry climate during the period since c. 130 ka ago. The particle‐size distribution pattern of the upper section was similar to that of the Xiashu loess, while that of the middle to lower section was similar to those of fluvially reworked red earth. A rapid increase in the abundance of large grain‐size components at 2.6 m depth indicates an intensification of the winter monsoon and a cool and dry climate during the period, in good agreement with results from the clay mineral composition and homogeneous structure. The red earth sequences in south China could probably be used to test the response of tropical to subtropical regions to global climate changes.     

相山矿田热液水云母化及其与铀矿化关系研究

相山铀矿田广泛发育热液水云母化,且水云母以伊利石、蒙皂石混层矿物居多。对典型矿床围岩、蚀变岩石和矿石中粘土组成的定量分析和化学成分分析表明：随着Ｕ元素的逐渐富集,粘土矿物存在蒙皂石→伊利石、蒙皂石混层矿物→伊利石的转化过程,而且这一转化过程在本区是一个动态的平衡过程,这一研究结果很好解释了相山矿田以群脉矿床的为主的特征;蚀变岩石中高蒙皂石含量的粘土矿物为后期富大矿起了富集Ｕ的作用。     

重庆涪陵二龙口剖面P—T界线附近黏土矿物特征及其古环境意义

在二叠系—三叠系界线附近地层中,利用大气暴露面上沉积物恢复古环境的研究至今尚未展开.四川盆地东部涪陵地区的二龙口剖面在二叠纪末位于扬子碳酸盐岩台地内,为礁后开阔台地相,在上二叠统—下三叠统界线附近沉积了较为完整的海相碳酸盐岩.该地层从下到上可分为1～31层.其中,上二叠统长兴组(1～6层)顶面为侵蚀不整合面,下伏于厚3～10cm(平均厚度约5cm)的古风化壳(7层).相较于1～6层,飞仙关组7～19层中碳酸盐矿物含量降低,黏土矿物含量增高.而20～31层以泥晶灰岩为主,偶尔伴有薄层黏土岩夹层.二叠系—三叠系界线位于19～20层之间.岩石学和矿物学特征显示,风化壳以黏土矿物为主,主要为规则伊蒙混层(I/S)和少量伊利石.在扬子台地范围内不同的沉积相带中,该黏土矿物组合具有较好的地层可对比性,说明研究区长兴组之上风化壳中黏土矿物形成的主控因素可能是区域性的,如火山活动带来的外源沉积.结合其下伏围岩(1～6层)岩石学和稳定同位素组成均缺乏淡水改造特征,可以判断该风化壳形成于加积模式而非改造模式.值得注意的是,此种黏土矿物以规则伊蒙混层和伊利石为主的组合方式,与二叠纪末出现的碱性、高温、缺氧的沉积环境一致.自7层向上,黏土矿物中伊蒙混层相对含量逐渐降低,且混层比逐渐减小,而伊利石、绿泥石、绿蒙混层相对含量逐渐增加,则与逐渐加剧的碱性-高温-缺氧的极端沉积环境有关.因此,二叠系—三叠系界线附近黏土矿物对扬子台地二叠纪末古环境突变有较好的记录能力.     

Palaeoenvironmental significance of the clay mineral composition of Olduvai basin deposits,northern Tanzania

Quaternary deposits in the southeastern part of the Olduvai basin, northern Tanzania, consist of lake margin deposits, followed by a series of fluvial sediments. The clay mineral fraction of the lake margin deposits (Bed I and lower part of Bed II) is composed of smectite and subordinate illite. All smectite is largely dioctahedral and shows indications for a limited degree of irregular interstratification by illite. In the overlying fluvial deposits (Beds II–IV), illite is the most abundant clay mineral. Smectite only occurs in lower parts of the fluvial deposits (up to the middle of Bed III), where it generally shows a high degree of irregular interstratification. Differences in clay mineral composition between the lake margin deposits and the fluvial deposits record differences in sediment source area and degree of alteration. Dioctahedral smectite in the lake margin deposits and the oldest fluvial deposits is derived from a region with volcanic material extending to the east and south of the basin, which also supplies a certain amount of illite. Illite in the fluvial deposits of Bed IV originates from an area with a metamorphic bedrock to the west and north. Alteration of detrital clay minerals resulted in Mg-enrichment of dioctahedral smectite in part of the lake margin deposits and partial illitization of smectite in the older fluvial deposits. Formation of clay minerals during diagenesis or soil development is not documented by analysis of the total clay fraction.     

Evidences of felsic volcanism and hydrothermal activities from clays associated with the Palaeoproterozoic Porcellanite Formation of the Vindhyan Supergroup,Central India

Chemico-mineralogical attributes of authigenic clays associated with the altered volcanic tuffs that occur in the Palaeoproterozoic Porcellanite Formation contain evidences of hydrothermal alteration and diagenetic processes in a marine environment. Previous sedimentological and geochemical studies on Porcellanite Formation were restricted to the Chopan area, but, the details related to provenance, nature and source of volcanism archived in these clays have not been ascertained. In order to understand these aspects, present study on these authigenic clays were carried out. Clay minerals represent dominance of illite with subordinate amount of montmorillonite. Moreover, low abundance of kaolinite is also noticed. The illite fibers and plates associated with the kaolinite indicate illitization. The kaolinite to illite transformation is favoured by incorporation of K⁺ ions, derived from the K-feldspar dissolution and its overgrowth. Major oxide contents of these clays and their ratios when plotted over diagrams marked with standard illite, kaolinite, smectite and chlorite compositional fields show clustering within or close to the illite field. Thermodynamic components calculated for these clays when plotted over AR₂³⁺AlSi₃O₁₀(OH)₂ − R₂³⁺Si₄O₁₀(OH)₂ − AR²⁺R³⁺Si₄O₁₀(OH)₂ ternary diagram, data plots lie within the illite, mixed layer I/S and smectite fields. Binary major oxide data plots between bulk rock and authigenic clay compositions showed felsic affinity. Montmorillonite and illite predominated in the eastern and western marginal areas of the Vindhyan Basin, respectively. However, former resulted from the hydrothermal alteration of volcanic glass associated with the ferruginous breccia and altered tuffs and remnants of the volcanic vents, whereas, later is associated with the tuffaceous beds. Owing to the adsorption, Ba, Rb and Sr is enriched in clays comparing to the bulk rock composition. Low (< 15 ppm) Sc values suggested major contribution from the felsic component. Also, low Rb/Sr and Th/U values revealed moderate insitu weathering. The dominance of K-feldspar alteration and insitu weathering is also evident from clustering of clay data plots in the A-CN-K ternary diagram. Pronounced negative Eu anomaly together with higher LREE/HREE values associated with these clay minerals implied proximity to source and their possible derivation from the silicified felsic tuffs available in the provenance.     

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。     

蒙皂石伊利石化反应机理和框架性行为模式

对珠江口盆地两口钻井95个泥质岩样粘土矿物X衍射分析资料的定量研究表明,若反应是以消耗蒙皂石为代价形成伊利石,则反应符合溶解-沉淀机理,但除此以外,蒙皂石还可以净溶解或新增伊利石层的方式加大I/S比。蒙皂石在渐进成岩过程中的框架性行为模式具有三级控制,按顺序分别由温度、基本离子成分和动力学因素控制特定温度段内蒙皂石行为过程的起始和终结、行为过程的方式和行为过程的速率和程度。渐进成岩过程中I/S比的变化主要与第三级控制有关,而游离状蒙皂石和伊-蒙混层粘土的含量变化则是第二三两级共同控制的结果。     

蒙脱石伊利石化的水热实验模拟

以蒙脱石为初始材料,通过水热实验模拟在不同温度压力条件下蒙脱石的伊利石化过程。利用X射线粉末衍射及X射线荧光光谱、红外光谱和扫描电镜等方法对样品的矿物物相、化学成分、晶体结构与微观形貌等进行分析,其结果表明:(1)蒙脱石至伊利石的转化受温度和压力条件的控制;(2)随着温度和压力的增高,蒙脱石伊利石化沿着蒙脱石-无序伊蒙混层-有序伊蒙混层-伊利石的转化序列进行转化;(3)水热实验模拟表明蒙脱石至伊利石的转化以溶解重结晶机制为主。实验结果不仅有助于了解埋藏与低级变质作用中的蒙脱石伊利石化过程,同时为研究断层活动所致断层泥中黏土矿物的转化及反演断层形成时温度压力条件提供基本参数。     

Mineralogical characteristics of upper Jurassic Mikulov Marls,the Czech Republic,in relation to their thermal maturity

The Upper Jurassic Marls of Mikulov present a formation that is considered to be the most promising strata to produce hydrocarbons in the Vienna basin. The marls are composed of dark pelagic marlstones that frequently contain layers of limestone with thickness reaching several hundreds of meters. Twenty-seven core samples from selected wells located in the south-eastern portion of the Czech Republic representing depths ranging from 2300 to 4500 m were analyzed by x-ray diffraction to assess bulk mineralogy and the progress of smectite illitization.Bulk mineralogy of the Mikulov Marls comprises carbonates (mean value = 54.4 mass%), clay minerals (26.6 mass%), quartz (15.0 mass%), and feldspar (1.6 mean%). In the decreasing order, the clay mineral fraction is composed of illite/mica, kaolinite, illite-smectite, and chlorite. The amount of smectite in illite-smectite decreases with depth from 70% to 28%. There is a change from random to ordered interstratification at the depth of 3300 m. The transition from short-range ordering (R1) to long-range ordering (R3) occurs at depths greater than 4,500 m.There was a good correspondence between thermal maturity parameters: the percentage of smectite in illite-smectite structures and vitrinite reflectance as a parameter of organic matter. The increase of the metamorphic grade was compared in respect to the geothermal gradient with adjacent basins.     

下扬子区早三叠世风暴沉积的粘土矿物分析

通过对下扬子区泾县、宁国、宜兴等地早三叠世风暴沉积中的粘土矿物进行取样分析,并综合沉积学和古生物学等特征的研究表明：随着Kübler指数的增高,所测样品中蒙皂石的含量呈递减趋势,蒙皂石伊利石化明显受阻,并且风暴沉积的各层段粘土矿物组合特征也相差较大,其主要因素是物源的变化。根据沉积特征和粘土矿物组合中蒙皂石和伊利石等含量的不同,可将本次研究的剖面分为两个序列:序列Ⅰ以宁国和宜兴等地为代表,为近源型风暴沉积;序列Ⅱ以泾县为代表,出现了近源和远源的双重属性,究其原因可能是因泾县位于近源和远源沉积的过渡带所致。     

A short range interaction model applied to illite/smectite mixed-layer minerals

We present a solid solution model, able to take into account short-range interactions up to the third nearest neighbor. This model has been applied to illite/smectite mixed-layer clay minerals and tests the relative thermodynamic stability of each illite/smectite stacking sequence. The non-ideal energy terms have been calculated, showing a strong decrease of the interaction energy as the distance between elements grows. From ΔG _m calculations the model predicts the following succession in I/S stacking sequences as X _i tends to 1:R1, R2 and then R3. This succession agrees well with some mineralogical observations in natural series. Received: July 12, 1996 / Revised, accepted: March 21, 1997