Discrete clay diagenesis in a very low-permeable sequence constrained by an isotopic (K–Ar and Rb–Sr) study

Multimethod analyses of several size fractions of clays were used to reconstruct the diagenetic history of the shallow buried claystones within the Paris Basin. A systematic decrease occurred in K-Ar dates relative to the decrease in size of the clay fractions, signifying higher amounts of newly formed clay material in the finer fractions. We suggest that the authigenic clay minerals occurring in the fine fractions had an Al-montmorillonite composition. By assuming that the isotopic K-Ar and Rb-Sr dates obtained on a bentonite layer in the sedimentary sequence stand for pure, authigenic clay minerals, one may interpret all K-Ar dates as mixtures of one authigenic and two detrital end-members. The results imply that a period of low sea level favoured diagenetic smectite-type clay formation about 10-15 million years after deposition of the sediments. Signatures of limited-scale chemical and isotopic homogenisation mean that the rock volumes affected by the diagenetic modifications had to be quite limited. The study of clay minerals extracted from some stylolites further suggests that any overpressure related to the origin of stylolites had no effect on clay authigenesis.     

油气储层自生伊利石的分离提纯及其K-Ar同位素测年技术研究

油气注入史研究对于指导油气勘探具有非常重要的意义。油气储层自生伊利石K Ar同位素测年可以为油气注入时间的研究提供科学依据。文中对油气储层自生伊利石分离提纯及其K Ar同位素测年技术进行了系统介绍。对碎屑含钾矿物杂质对自生伊利石K Ar同位素年龄的影响进行了深入研究 ,建立了一套完整的数据处理技术并提出了“校正年龄”的概念。     

Diagenesis of the Lower Cretaceous Kanmon Group sandstones, SW Japan

The Kanmon Group (Lower Cretaceous) is a non-marine sequence in the Inner Zone of southwest Japan and is divided into the lower Wakino (lacustrine) and the upper Shimonoseki (fluvial) subgroups. Major diagenetic changes in this group are compaction, iron-oxide cementation, calcite cementation and grain replacement, quartz overgrowth and pore-fill cementation, illite authigenesis, chlorite pore-fill cementation and grain replacement, albitization of feldspar, and grain replacement by pyrite. Two subgroups of the Kanmon Group present no significant differences in general diagenetic features, paragenetic sequence, or the degree of diagenetic changes despite differences in depositional environments (lacustrine vs. fluvial) and stratigraphic positions. However, some differences are recognized in the content and chemistry of authigenic minerals caused by different sandstone framework compositions. The content of authigenic clay minerals is higher in sandstones of the Shimonoseki Subgroup containing abundant volcanic rock fragments. In addition, the composition of chlorite, the most abundant authigenic clay mineral in Kanmon sandstones, is Mg-rich in the volcanoclastic Shimonoseki sandstones, compared to an Fe-rich variety in Wakino sandstones. The original sandstone composition played a significant role in pore-water composition and diagenetic reactions.The Wakino sandstones lost most of its porosity by compaction, whereas Shimonoseki sandstones are only compacted in the vicinity of the basin-bounding fault. The weakly compacted Shimonoseki sandstones, instead, were largely cemented by pore-filling calcite during early diagenesis; cementation prevented compaction during further burial. The Kanmon Group sediments were heated to about 300 °C based on illite crystallinity values.     

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。     

松辽盆地晚白垩世粘土矿物特微及沉积环境分析

松辽盆地晚白垩世地层是由一套砂泥岩组成,储集了丰富的石油资源。过去一般认为这是一个内陆湖泊,为陆相沉积。近年来不少研究者从古生物、岩矿等方面提出与海有关的成因观点。本文根据对该区上白垩统泥岩粘土矿物进行了研究后认为,晚白垩世松辽盆地是个近海陆盆,气候温暖干燥,间转湿润,以淡水-半咸水碱性介质为主,青山口组及嫩江组沉积时,水域扩大,水体含盐度、碱性、还原性增强,可能遭受海侵。这些分析对含油地层的成因研究具有一定的意义。     

Early formation of K-feldspar in shallow-marine sediments at near-surface temperatures (southern Israel): evidence from K-Ar dating

Authigenic K‐feldspar was investigated in two Albian to Turonian sections in Israel using K‐Ar and Ar‐Ar dating, X‐ray diffraction, scanning electron microscopy and chemical analysis. Both sections comprise a similar succession of shallow‐marine limestones, dolomites and marls, with some sandstone and shale beds of continental origin. The HCl‐insoluble residue fraction of the studied samples consists of clays, quartz, feldspars, goethite and trace amounts of heavy minerals. Most of the insoluble residues have a relatively high K‐feldspar content that has an adularia habit and is concentrated in the 4–7 µm size fraction. The authigenic origin of the K‐feldspar in the fine silt fraction is indicated by its high content relative to quartz, the uniform and idiomorphic shape of the crystals and its limited size range. Of the fine silt (4–7 or 4–10 µm) separates, 40% have ages that are similar to stratigraphic ages within the analytical and biostratigraphic errors. Ar‐Ar dating of a fine silt fraction with 94% K‐feldspar (4–10 µm, sample GYP 7) yields a plateau age identical to the total gas age and similar to the stratigraphic age. These results indicate that the K‐Ar age is not a mixture between detrital and late diagenetic K‐feldspar ages, but is rather an age of formation within a few million years after deposition. It is suggested that the early formation of the K‐feldspar was associated with dolomitization and was induced by residual brines as part of a reflux process.     

K–Ar dating of authigenic minerals in siliciclastic sequences: an example from the south Sanfranciscana Basin (Western Minas Gerais,Brazil)

K–Ar dating was applied on authigenic potassic minerals which are abundant in sandstones from the south of the Sanfranciscana Basin, Western Minas Gerais State, central Brazil. The Quintinos Member fluvial sandstones (Três Barras Formation, Areado Group) contain significant amounts of authigenic K‐feldspar as microcrystals of adularia and sanidine habits. The ages of these microcrystals cluster into three groups: 106.1 ± 2.2, 89.9 ± 1.9 and 88.8 ± 1.8 Ma (from Albian to Coniacian). The older age of 106.1 ± 2.2 Ma was obtained from the coarse fraction analysed (10–20 µm) that can contain a mixture of detrital potassic minerals (K‐feldspar, muscovite, biotite and illite) and different authigenesis of K‐feldspar (overgrowths and microcrystals). Thus, only the younger ages were interpreted as precipitation of K‐feldspar microcrystals during the Late Cretaceous into the Quintinos Member sandstones. Moreover, these ages can document the formation of microcrystals within a few million years after deposition of the sandstones. The ages of authigenic illite from the Capacete Formation epiclastic sandstones (Mata da Corda Group) range from 88.5 ± 1.9 to 71.5 ± 1.9 Ma (Coniacian–Campanian). These results suggest the timing of the illitization event in these sandstones as well as a synchrony with K‐feldspar authigenesis in the Quintinos Member sandstones. These results are well constrained and are in agreement with stratigraphic, biostratigraphic and radiometric ages previously reported for the Sanfranciscana Basin. Copyright © 2014 John Wiley & Sons, Ltd.     

塔里木盆地西北缘下寒武统黑色岩系差异性成岩演化及其影响因素

尽管泥页岩在埋藏过程中经历的复杂成岩改造会显著影响页岩油气储层发育潜力,但对其成岩作用,特别是泥页岩中成岩矿物的类型、成岩演化及其影响因素、成岩矿物元素在低孔低渗孔隙系统中的迁移等问题的认识仍很薄弱,因而制约了对泥页岩储层的深入认识。为此,本文以塔里木盆地西北缘下寒武统玉尔吐斯组发育的两套黑色岩系为例,在沉积环境认识的基础上,通过矿物组分、黏土矿物组合、有机碳含量及有机质成熟度等测定分析,着重研究了黑色岩系自生矿物的分布及在成岩演化阶段的变化特征,阐述了成岩变化的时空分布及其影响因素。研究结果表明：（1）在浅水缓坡台地环境下,玉尔吐斯组受两个较为完整的海进-海退沉积旋回控制而形成的两套黑色岩系主要经历了早成岩阶段和中成岩阶段;（2）受沉积环境和热液作用的影响,这两套黑色岩系在石英、重晶石、碳酸盐胶结物和黏土矿物等自生矿物的组合、分布及形成顺序上存在显著的差异,呈现出差异性成岩演化的特点;（3）伊利石、伊蒙混层、绿泥石、白云石、石英胶结等中成岩阶段成岩产物的广泛分布,反映出在成岩过程中特别是中成岩阶段低孔低渗的泥页岩仍存在一定程度的内部和外部来源的矿物元素迁移。本次研究对深入认识塔里木西北缘下寒武统黑色岩系成岩机制,以及分析页岩储层发育特征提供了重要的依据。     

Glauconites from the Late Palaeocene — Early Eocene Naredi Formation,western Kutch and their genetic implications

Glauconitic minerals are considered as one of the valuable input parameters in sequence stratigraphic analysis of a basin. In the present study glauconitic minerals are reported from subtidal green shale facies in the lower part of the Late Paleocene-Early Eocene Naredi Formation of western Kutch. On the basis of the foraminiferal assemblage the glauconite bearing beds are interpreted to have formed in a mid shelf depositional settings of an unstable marine conditions. XRD studies confirm the glauconite mineralogy of the green pellets and provide an estimation of glauconite maturity. Textural attributes of the glauconites confirm their derivation by different degrees of alteration of precursor feldspar grains. Because of the authigenic origin and autochthonous nature, these glauconites hold promise for understanding sequence stratigraphy of the Palaeogene succession of the western Kutch.     

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。     

粘土矿物研究在塔里木盆地石油勘探中的应用

以塔里木盆地粘土矿物的分布特征及其组合形式、演化与形成机理为依据,探讨了粘土矿物在地层划分对比中的应用及其与有机质热演化、成岩阶段的关系和对储层物性的影响。研究表明,在侏罗系和白垩系两个不同古环境中形成的粘土矿物及其组合特征,为地层对比提供了一定的证据。泥岩中伊利石／蒙皂石间层中蒙皂石含量的纵向变化与有机质热演化及成岩阶段的关系不大。对储层物性影响不大但有利于储集性能的是以高岭石为主的粘土矿物组合类型及粘土矿物的早期自生（伊利石／蒙皂石间层矿物）衬垫式以及非自生（伊利石）衬垫式产状。     

Dating multistage paleofluid percolations: A K-Ar and O/O study of fracture illites from altered Hercynian plutonites at the basement/cover interface (Poitou High, France)

Isotopic age determination of fluid events in basement fractures is of prime importance for the reconstruction of paleo-hydraulic regimes. However, material from fracture or wall-rock is not generally easily dated. In the case of fractures filled by minerals such as phyllosilicates, it can be expected that subsequent fluid circulation may cause partial alteration or recrystallization of the previous phyllosilicates, disturbing the isotope signature. Using a specific methodology, including the extraction process without contamination of the finest (<0.2 μm) authigenic fractions, identification of clay fractions by X-ray diffraction (XRD), scanning electron microscopy, and electron microprobe, analysis of stable isotope composition (D/H, δ¹⁸O) and K-Ar dating, fluid event ages can be estimated. This methodology was applied to the northwestern margin of the French Massif Central, where basinal brines have interacted with the sedimentary cover (infra-Toarcian formations) and the fractured Hercynian crystalline basement. During periods of unknown age, precipitates from brines sealed most basement fractures as carbonates, and a recrystallization of early Hercynian phengite (+chlorite) into illite and illite/smectite minerals occurred in the earlier fractures.XRD patterns show that the clay fraction is dominated by illite and ordered mixed-layer minerals having a relatively high amount of illite (I-S R3). In the shallowest samples beneath the paleo-surface, a late assemblage is identified as a mixture of I-S minerals, a part of them being characterized by significant amounts of swelling layers (I-S R0).The δD values of the clay fractions are fairly constant around −50 ± 10‰, but δ¹⁸O values of the same clay fractions display a wide range from 8‰ to 18‰ (SMOW). The study of the size fractions between 2 and 0.2 μm reveals a correlation between K-Ar ages and δ¹⁸O values, which cannot be related to a change in the relative amounts of clay minerals. Deep fractures (at depths of 570 and 923 m) are characterized by δ¹⁸O values around 10.3 ± 0.4‰ SMOW and old ages ranging from 253 to 272 Ma. The finest fractions (<0.2 μm) of clays located at shallow level (<300 m) beneath the paleo-surface yield the highest δ¹⁸O values (15.7-18.2‰) and the youngest K-Ar dates (188 to 198 Ma). These dates are likely to record the extensional episode and thermal anomaly related to the rifting of central Atlantic Ocean (c. 190 Ma). The other important thermal/extensional episode which affected the Aquitaine Basin, namely the opening of the Gascogne gulf at c. 120 Ma, is not detected by the K-Ar method on the clay fractions. We believe that resetting of clay-type K-Ar ages linked to recrystallization was favoured in the upper part of the basement where the ancient (Hercynian) clay minerals were destabilized by subaerial low-temperature alteration during Permo-Triassic times.From a methodologic point of view, the analytical characterization of several size fractions of clays from reactivated fractures, using both stable isotope geochemistry and K-Ar isotope geochemistry, can be considered as a powerful tool for dating fluid events when no suitable material for conventional methods is available.     

国内难溶性钾矿资源及其开发利用

国内难溶性钾矿资源较丰富,可分为含钾岩石和含钾矿物两大类及若干亚类。含钾沉积岩有:富钾火山沉积凝灰岩(绿豆岩),含钾砂、页岩,含钾泥灰岩,含钾石膏泥,含钾磷块岩等;含钾岩浆岩有:霞石正长岩、霓辉石石英正长岩、流纹斑岩、正长斑岩、花岗伟晶岩、钾长粗面凝灰熔岩等;含钾变质岩有:钾长浅粒岩、云母片岩、钾长混合片麻岩等;可作钾矿资源的含钾矿物有:钾长石、明矾石、伊利石、白榴石、海绿石等。目前,绿豆岩,含钾砂、页岩,流纹岩,海绿石,白榴石等已可单独开采利用,制作钾肥;霞石正长岩、伊利石、钾长石、明矾石等可被综合回收利用;粗面岩、响岩、粗玄岩,含钾泥灰岩、钾长浅粒岩等尚待开发利用。     

The effects of diagenesis on the reservoir characters in sandstones of the Late Cretaceous Pab Formation,Kirthar Fold Belt,southern Pakistan

The Maastrichtian Pab Formation in the southern part of Pakistan is composed of fine- to very coarse-grained texturally mature quartz arenite and subordinate sublitharenite varieties. The sandstones have undergone intense and complex diagenetic episodes due to burial and uplift. Diagenetic modifications were dependent mainly on the clastic composition of sandstone, burial depth and thrust tectonics. Diagenetic events identified include compaction, precipitation of calcite, quartz, clay minerals and iron oxide/hydroxide, dissolution and alteration of unstable clastic grains as feldspar and volcaniclithic fragments as well as tectonically induced grain fracturing. The unstable clastic grains like feldspar and lithic volcanic fragments suffered considerable alteration to kaolinite and chlorite. Dissolution and alteration of feldspar and volcanic lithic fragments and pressure solution were the main sources of quartz cements. Mechanical compaction and authigenic cements like calcite, quartz and iron oxide/hydroxide reduced the primary porosity, whereas dissolution of clastic grains and cements has produced secondary porosity. Chlorite coatings on clastic grains have prevented quartz cementation. Coarse-grained, thick bedded packages of fluviodeltaic, shelf delta lobe and submarine channels facies have higher average porosity than fine-grained, thin bedded and bioturbated sandstone of deeper shelf and abyssal plain environments and these facies are concluded to be possible future hydrocarbon prospects.     

The effects of diagenesis on the redistribution of strontium isotopes in shales

The rubidium-strontium method has often been used in attempts to date shales, but has yielded mixed results. In order to explore the effects of diagenesis on this system, samples of a Miocene shale section collected from an oil well drilled in coastal Louisiana were separated into fractions and analyzed for Sr⁸⁷/Sr⁸⁶, Rb and Sr. The diagenetic changes involve the destruction of detrital mica and feldspar and the formation of an illite-rich clay from smectite. Strontium from interstitial waters, calcium carbonate and adsorbed on the clay minerals is released and then sequestered by the newly forming phases, together with the strontium mobilized from the silicate minerals. Attending these changes there is a trend towards the homogenization of the shale with respect to its strontium isotopes, but diagenesis and homogenization are not complete in the deepest part (5523 m) of the section studied. Therefore, the interpretation of rubidium-strontium shale dates remains uncertain, but the dates in many cases most probably represent the time equal to or younger than the time of the major construction of new phases and the attendant homogenization of the strontium isotopes.     

松辽盆地南部HX井上白垩统青山口组黑色泥岩的矿物组成与自生微晶石英成因

泥质岩的矿物组成和成岩作用是制约其作为CO₂地质封存的盖层封闭能力和作为页岩气储层具易压裂性质的重要原因。通过地球化学分析、X-射线衍射分析和扫描电镜观测及能谱测定,确定了松辽盆地南部HX井上白垩统青山口组泥岩的矿物组成,识别出了蒙皂石转变伊利石反应过程中形成的亚微米级自生微晶石英。研究表明：HX井上白垩统青山口组泥岩的母岩岩石类型和风化效应一致,泥岩主要由黏土矿物、钠长石和石英组成,钾长石少量;黏土矿物以伊利石/蒙皂石混层为主,其次为绿泥石;脆性矿物（钠长石、石英和钾长石）的平均质量分数为44.43%,黏土矿物平均质量分数为54.26%。蒙皂石转变伊利石反应过程中形成的亚微米级微晶石英单晶呈自形－半自形粒状,集合体呈巢状,分布于伊利石/蒙皂石混层黏土矿物的微孔隙中。以伊利石/蒙皂石混层矿物为主、且存在一定量的自生微晶石英的泥岩盖层（例如HX井青山口组泥岩）将有助于注入CO₂的长期封存。HX井青山口组泥岩中的脆性矿物含量符合工业价值页岩气的储层标准,而黏土矿物含量则相差较多。     

鄂尔多斯盆地白垩系粘土矿物的分布特征及其沉积-成岩环境意义

系统地分析了鄂尔多斯盆地白垩系粘土矿物的特征及其沉积、成岩环境意义。研究结果表明:白垩系砂岩、泥质岩的粘土矿物组合以I+C+I/S型、I+C型为主,具有高伊利石含量,较高绿泥石、伊/蒙混层矿物含量的粘土矿物组成特点;其中泥质岩粘土矿物主要为陆源碎屑成因,次为沉积成岩过程中形成的自生粘土矿物,而砂岩粘土矿物兼有陆源碎屑成因和沉积成岩过程自生成因的特征;白垩系沉积时气候总体特征为干旱—半干旱,但局部时段发生干—湿气候波动而处于短暂的湿热气候环境;白垩系沉积物源富含长石等硅酸盐矿物,沉积物质主要自北、南、西向盆地内部搬运沉积;白垩系沉积和埋藏成岩过程中水介质整体上具有盐度较高,偏碱性,富K+、Fe2+、Mg2+的特点,且总体上盆地南部水介质中的这些指标都高于北部。     

Authigenic quartz and albite in Devonian limestones: origin and significance

Euhedral quartz and albite crystals are common in Devonian (Givetian-Frasnian) shallow-marine shelf carbonates from the Belgian Ardennes. Several features such as morphology, the presence of carbonate inclusions, inversion temperatures and occurrence in the insoluble residues of stylolitic surfaces indicate that these crystals have developed authigenically. Oxygen isotope ratios point to an intermediate deep burial realm of origin at temperatures of 60–90°C. The predominance of illite and the almost total absence of smectite clay minerals is interpreted as an indication that illitization produced the silica needed for authigenesis. The mineral composition of inclusions indicates that the carbonate host rock must have consisted of low-Mg calcite already at the time of authigenesis. These inclusions represent an earlier diagenetic stage than the present carbonate rock, since they were protected from further diagenetic alteration by the surrounding quartz. The calcite inclusions display a higher Sr/Ca and Mg/Ca ratio than the carbonate host-rock. Because neomorphic diagenesis of the carbonate continued after silicate authigenesis, the contents of Mg and Sr in the calcite of the host carbonate are even lower. The authigenic feldspar mineralogy seems to be determined by the composition of the host-sediment.     

Problems with argon: K-Ar ages in Gulf Coast shales

K-Ar ages of Gulf Coast shales do not correspond to diagenetic ‘events’, but are a combination of inherited detrital ages and authigenic overprints. The key to understanding K-Ar ages of shales is the fate of the ⁴⁰Ar when the host minerals dissolve or react during the illitisation reaction: is ⁴⁰Ar incorporated within the illite, or is it lost to the porewaters? Ages are modelled as due to a single illitisation reaction, assuming a uniform precursor sediment and open-system import of K. Both whole-rock and clay mineral fraction data can be reproduced by modelling. The ⁴⁰Ar incorporated into illite is a surprisingly high proportion (75-100%) of that produced within detrital phases (smectite, K-feldspar, mica), perhaps implying that the illitisation reaction is a solid-state transformation, or that ⁴⁰Ar is imported into the shales along with incoming K. The model does not provide a good fit to the data below 4000 m, when the illitisation reaction is apparently complete, but shales lose ⁴⁰Ar by solid-state diffusion or recrystallisation.     

Inclined K–Ar illite age spectra in brittle fault gouges: effects of fault reactivation and wall‐rock contamination

K–Ar clay fraction ages of brittle faults often vary with grain size, decreasing in the finer size fractions, producing an inclined age–grain‐size spectrum. K–Ar ages and mineralogical characterization of gouges from two normal faults in the Kongsberg silver mines, southern Norway, suggest that inclined spectra derived from brittle fault rocks reflect the mixing of inherited components with authigenic mineral phases. The ages of the coarsest and finest fractions constrain faulting at c. 260–270 Ma and reactivation around 200–210 Ma, respectively. This study demonstrates how wall‐rock contamination influences the K–Ar age of the coarsest size fractions and that authigenic illite and K‐feldspar can crystallize synkinematically under equivalent conditions and thus yield the same K–Ar ages.