Formation of corrensite, chlorite and chlorite-mica stacks by replacement of detrital biotite in low-grade pelitic rocks

Transmission and scanning electron microscopy were utilized to investigate the nature and mechanisms of alteration of abundant detrital biotite of volcanic origin and progressive modification of phyllosilicate aggregates in a prograde sequence of pelitic rocks (illite crystallinity index = 0.19–0.58λ2θ) from the Gaspé Peninsula in Quebec.
Detrital biotite has been diagenetically altered to form corrensite and chlorite through two mechanisms; (1) layer-by-layer replacement gave rise to interstratification of packets of layers and complex mixed layering via several kinds of layer transitions between biotite and chlorite, corrensite or smectite; (2) dissolution-transport-precipitation resulted in the formation of relatively coarse-grained aggregates of randomly orientated, corrensite-rich flakes and fine-grained corrensite intergrown with chlorite and illite in the matrix.
The data show that stacks consisting of alternating packets of trioctahedral and dioctahedral phyllosilicates originated during early diagenesis when lenticular fissures in strained altering biotite were filled by dioctahedral clays. Subsequent prograde evolution of dioctahedral clays occurred through deformation, dissolution and crystallization, and overgrowth. Illite evolved to muscovite, with K in part provided through biotite alteration, and corrensite/chlorite to homogeneous chlorite. The alteration of detrital biotite is closely related to the formation of titanite and magnetite in diagenetic rocks, and pyrite, calcite and anatase or rutile in the higher grade rocks.
The observations demonstrate that detrital biotite of volcanic origin may be the principal precursor of chlorite in chlorite-rich metapelites originating in marginal basins. The mineral parageneses suggest that the transitions from corrensite to chlorite and illite to muscovite may be a function of local chemistry and time.     

Strain-related differences in the crystal growth of white mica and chlorite: a TEM and XRD study of the development of metapelitic microfabrics in the Southern Uplands thrust terrane, Scotland

Abstract TEM and XRD techniques were used to study crystal growth characteristics of the fabric-forming phyllosilicates which developed in response to low-grade metamorphism and tectonic imbrication in part of the Southern Uplands thrust terrane. Prograde regional metamorphism, ranging from late diagenesis through the anchizone to the epizone, was accompanied by the development of a slaty cleavage which is commonly bedding-parallel. TEM-measured mean thicknesses of white mica and chlorite crystallite populations increase with advancing grade and correlate with XRD-measured crystallinity indices. Analytical TEM data show that prograde changes in composition lead to a net loss of Si, Ca and minor Fe from the fabric-forming phyllosilicates. White micas are paragonite-poor phengites with a mean b lattice parameter of 9.037 Å, and indicate an intermediate pressure series of metamorphism with a field gradient of <25° C km^-1. Chlorite compositions evolved from diabantite (with intergrown corrensite) to ripidolite over an estimated temperature range of 150–320° C. Field gradient and temperature estimates suggest that crystal growth and fabric development occurred at burial depths ranging from 6 km to at least 13 km in the thrust terrane. During late diagenesis, crystal growth of white mica and chlorite was predominantly a consequence of polytypic and phase transitions, and resulted in similar size distributions which resemble typical Ostwald ripening curves. Under anchizonal and epizonal conditions, white mica grew more rapidly than chlorite because of its greater ability to store strain energy and recover from subgrain development; as a result crystal thickness distributions are not typical of Ostwald ripening. In contrast, chlorite crystals which grew under these conditions developed subgrain boundaries at high strain rates which were only partially recovered at low strain rates; these retained dislocations reduce the crystallite thicknesses detected by TEM and XRD, compared with those of white mica. These differences in strain-induced crystal growth indicate that white mica (illite) and chlorite crystallinity indices are likely to show significant differences where low-grade metamorphism is closely associated with tectonic fabric development.     

Phyllosilicates in hydrothermally altered basalts from DSDP Hole 504B,Leg 83 — a TEM and AEM study

Phyllosilicates occurring as replacements of olivine, clinopyroxene and interstitial materials and as veins or fracture-fillings in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 have been studied using transmission and analytical electron microscopy. The parageneses of phyllosilicates generally change systematically with depth and with the degree of alteration, which in turn is related to permeability of basalts. Saponite and some mixed-layer chlorite/smectite are the dominant phyllosilicates at the top of the transition zone. Chlorite, corrensite, and mixed-layer chlorite/corrensite occur mainly in the lower transition zone and upper levels of the sheeted dike zone. Chlorite, talc, and mixed-layer talc/chlorite are the major phyllosilicates in the sheeted dike zone, although replacement of talc or ohvine by saponite is observed. The phyllosilicates consist of parallel or subparallel discrete packets of coherent layers with packet thicknesses generally ranging from< 100 Å to a few hundred Å. The packets of saponite layers are much smaller or less well defined than those of chlorite, corrensite and talc, indicating poorer crystal-linity of saponite. by contrast, chlorite and talc from the lower transition zone and the sheeted dike zone occur in packets up to thousands of Å thick. The Si/(Si+Al) ratio of these trioctahedral phyllosilicates increases and Fe/(Fe+Mg) decreases in the order chlorite, corrensite, saponite, and talc. These relations reflect optimal solid solution consistent with minimum misfit of articulated octahedral and tetrahedral sheets. Variations in composition of hydrothermal fluids and precursor minerals, especially in Si/(Si+Al) and Fe/(Fe+Mg) ratios, are thus important factors in controlling the parageneses of phyllosilicates. The phyllosilicates are generally well crystallized discrete phases, rather than mixed-layered phases, where they have been affected by relatively high fluid/rock ratios as in high-permeability basalts, in veins, or areas adjacent to veins. Intense alteration in basalts with high permeability (indicating high fluid/rock ratios) is characterized by pervasive albitization and zeolitization. Minimal alteration in the basalts without significant albitization and zeolitization is characterized by the occurrence of saponite±mixed-layer chlorite/smectite in the low-temperature alteration zone, and mixed-layer chlorite/corrensite or mixed-layer talc/chlorite in the high-temperature alteration zone. Textural non-equilibrium for phyllosilicates is represented by mixed layering and poorly defined packets of partially incoherent layers. The approach to textural equilibrium was controlled largely by the availability of fluid or permeability.Contribution No. 488 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan     

成岩带、近变质带与一维纳米级层状硅酸盐

运用X射线衍射分析技术，计算了成岩带、近变质带粘土矿物C^*方向的粒度。根据阿尔卑斯造山带前陆碎屑岩粘土矿物粒度与伊利石结晶指数的关系，推导出了伊利石、绿泥石、蒙脱石、伊蒙混层、高岭石和叶蜡石的c^*方向粒度变化趋势曲线。结果表明，大多数产于成岩带和近变质带的粘矿物其c6*方向粒工为几至几十纳米。成岩带和近为质带是一维天然纳为级土帮物的产地。     

Formation mechanisms of illite,chlorite and mixed-layer illite-chlorite in Triassic volcanogenic sediments from the Southland Syncline,New Zealand

Clay minerals from the three principal kinds of zeolitic sediments from the type area for zeolite facies alteration, the Triassic Murihiku Supergroup, Southland, New Zealand, have been studied by TEM. Bentonitic tuff consists largely of smectite and heulandite with minor illite; they occur as replacements of glass shards and are inferred to be direct alteration products of tuff alteration. Both analcime- and laumontite-rich tuffs contain chlorite, illite and mixed-layer illite-chlorite, including 11 mixed-layer sequences. Subhedral to euhedral phyllosilicate crystal shapes and other textural features imply that phyllosilicates crystallized from solution derived in part by dissolution of precursor smectite. Intralayer transitions involving illite and chlorite are inferred to be products of crystallization rather than direct alteration and replacement. Petrographically similar bentonitic and analcimized tuffs overlap each other in the stratigraphic section, supporting earlier observations that there is no systematic change in smectite relative to the illite plus chlorite derived from smectite in sections up to 8.5 km thick. The data imply that smectite may be metastable relative to illite plus chlorite. Permeability and fluid chemistry are inferred to be as significant as temperature in promoting reactions in clay minerals as well as zeolites during burial metamorphism.Contribution No. 436, from The Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan 48109     

Burial history determination of the Triassic succession of Central and Northern Tunisia using clay minerals

The Oued Belif 48 and Koudiat El Halfa 5 borehole samples have been analysed in order to reveal the mineralogical composition of the Triassic successions and their burial history within the geological evolution of the Tethysian southern margin. Oued Belif 48 borehole belongs to Nefza district which is a part of the “Nappe zone” (Tellian unit, north-western Tunisia). Koudiat El Halfa 5 borehole crosses the Koudiat El Halfa diapir (north–west of the north–south axis, Central Atlas). In this paper, the burial degree of evaporitic Triassic samples was determined by the “illite crystallinity” index and by the evolution of the other phyllosilicates, essentially chlorite, talc and illite/chlorite and illite/smectite mixed layers. The studied samples of the two boreholes are characterized by the presence of abundant clay minerals. The <2-μm grain-size fraction of the samples is mostly composed of illite, chlorite and smectite and may contain a slight percentage of swelling layers (illite/smectite and illite/chlorite). The illite crystallinity value measured on ethylene glycol solvated oriented mounts of the Oued Belif 48 samples oscillates globally between 1 and 2.5 characterizing the epizonal zone with a range of 300–400 °C temperatures. The measures of Koudiat El Halfa 5 samples crystallinity index show a value ranging from 2 to 4, which indicates the anchizone and early epizone burial stage (temperatures around 200 °C). These data can be explained by Miocene magmatic activities characterizing the Triassic material of Nefza district and also by burial phenomena effects.     

岩石变形对粘土矿物结晶生长影响的初步研究——以江西金山金矿为例

作为流体作用过程中水—岩反应的产物，粘土矿物可以帮助人们认识水—岩反应的机制和流体活动的特征。本文以江西金山金矿为例，通过对热液蚀变粘土矿物伊利石和绿泥石结晶度、平均结晶大小和晶格应变的测定，讨论了岩石变形对伊利石和绿泥石结晶生长差异的影响。在岩石应变较弱、水／岩比较小的糜棱岩带，伊利石的平均结晶大小与结晶度成负相关，而在岩石应变较强、水／岩比较大的超糜棱岩带，绿泥石的平均结晶大小与结晶度成正相关。由应变较弱的蚀变糜棱岩带到应变较强的蚀变超糜棱岩带，伊利石的结晶度有变小的趋势，而绿泥石的结晶度则基本保持不变。认为在成矿流体作用过程中，粘土矿物的形成和特点不仅受水／岩比的影响，而且在岩石变形过程中，岩石的应变和恢复速率也影响粘土矿物的结晶大小；伊利石和绿泥石平均结晶大小与其结晶度之间的关系可以反映岩石变形的机制和行为。     

Diagenesis and Very Low‐grade Metamorphism of the Upper Permian Yangjiagou Formation in Eastern Changchun,China: Evidence from Clay Mineral Geothermobarometers

The metamorphic conditions of the Upper Permian Yangjiagou Formation in eastern Changchun, China, were evaluated based on the mineral assemblage, illite crystallinity, illite polytypism,the b dimension of illite, and the chemical composition of chlorite. The pelitic rocks in the Yangjiagou Formation are characterized by illite + kaolinite + chlorite ± mixed-layer chlorite/smectite and detrital quartz + plagioclase. Illite in the formation has a crystallinity of 0.38-0.55 and comprises mixed 2 M_1 and1 M_d polytypes, indicating a metamorphic temperature of 200℃. Based on the chemical composition of chlorite and the chlorite geothermometer, we estimated diagenetic to very low-grade metamorphic conditions with temperatures of 185℃～204℃. The b dimension of illite varies from 8.992 A to 9.005 A.We used a mathematical algorithm to extend Guidotti and Sassi's(1986) diagram relating illite b dimension with temperature and pressure, and used this diagram, together with illite crystallinity and chlorite chemical composition, to semi-quantitatively estimate the formation pressure at1.2 kbar. These reveal that the Yangjiagou Formation has experienced very low-grade metamorphism.     

The Multistage Illite Evolution in Upper Proterozoic Claystones from the Srednii Peninsula,Murmansk Coast of the Barents Sea

Fine-grained clay subfractions (SFs) with a particle size of <0.1, 0.1–0.2, 0.2–0.3, 0.3–0.6, 0.6–2.0, and 2–5 m separated from the claystone of Upper Precambrian Pumanskaya and Poropelonskaya formations on the Srednii Peninsula were studied by transmission electron microscopy, X-ray diffraction, and Rb–Sr methods. All subfractions consist of the low-temperature illite and chlorite, and the contribution of chlorite decreases with diminishing particle size. The crystallinity index and I ₀₀₂/I ₀₀₁ ratio increase from coarse- to fine-grained SFs. The leaching by ammonium acetate solution and the Rb–Sr systematics in combination with mineralogical and morphological data indicate that illite in Upper Proterozoic claystone from the Srednii Peninsula was formed during three time intervals: 810–830, 610–620, and about 570 Ma ago. The first generation of this mineral with a low Rb/Sr ratio dominates in coarse-grained SFs while the second and third generations with a high Rb/Sr ratio prevail in fine-grained SFs. All of the three generations are known in the Poropelon claystone, whereas the Puman claystone contains only illite of the first and second generations. Geological processes responsible for the multistage illite evolution in claystones are discussed.     

Genetic and chemical relationships between berthierine,chlorite and cordierite in nodules associated to granitic pegmatites of Sierra Albarrana (Iberian Massif,Spain)

Chlorite and berthierine occur through alteration of cordierite within enclaves of metamorphic rocks transformed by the Sierra Albarrana pegmatites. The coexistence of both phyllosilicates allows us to study their stability relationships and to compare their chemical compositions. Samples showing incipient replacement of cordierite by small cryptocrystalline aggregates can be identified by X-ray diffraction (XRD) as berthierine with small quantities of chlorite. Electron Microprobe (EMP) analyses give mixed compositions of berthierine and cordierite. Samples with extensive replacement of cordierite by aggregates show similar characteristics to those with incipient replacement, but some small crystals are present. The last type of sample shows complete replacement of cordierite by crystals showing optical properties of chlorite and EMPA compositions coherent with chlorite or berthierine. Their XRD pattern corresponds to chlorite and their high resolution transmission electron microscopy (HRTEM) images only show perfect sequences of 14 Å lattice fringes. The cryptocrystalline aggregates of the samples with incipient and extensive replacement present coexistent areas of 14 Å and 7 Å lattice fringes that are intergrown at different levels: (1) large areas (> 1 m) of 7 Å layers; (2) packets of 7 Å layers between 14 Å layer areas, with visible 7 Å to 14 Å lateral changes; (3) random mixed-layers 7 Å/14 Å. Chlorite is the final stable product of alteration of cordierite, with berthierine as an intermediate metastable phase. Energy dispersive X-ray spectrometry microanalyses of 14 Å, 7 Å and (14+7) Å areas show lack of systematic differences in chemical compositions between both phyllosilicates which may be considered as true polymorphs.     

Relations between stages of diagenetic and metamorphic evolution and the development of a primary cleavage in the northwestern Moroccan Meseta

The metamorphic evolution of the studied region is determined by the illite crystallinity index and by the evolution of the other phyllosilicates, essentially chlorite and mixed-layer minerals. Several zones are described, at a regional scale, characterized respectively by a diagenetic, anchimetamorphic and epimetamorphic evolution. The estimation of total strain is approached by the type of the cleavage in greywackes. Mapping of all these parameters reveals, at the scale considered, a close relationship between metamorphism and strain, which is briefly discussed.     

Microtextural investigation (SEM and TEM study) of phyllosilicates in a major thrust fault zone (Monte Perdido, southern Pyrenees): impact on fault reactivation

Thrusting fault zone in foreland basins are characterized by highly foliated zones generally enriched in phyllosilicates which can play a major role on the mechanical behaviour of the fault. In this context, investigations of synkinematic clay minerals permit to determine the origin of the fluid from which they precipitated as well as the mechanisms of deformation. Our study is focused on clay mineral assemblages (illite and chlorite) in a major thrust fault located in the Monte Perdido massif (southern Pyrenees), a shallow thrust that affects upper cretaceous-paleocene platform carbonates and lower Eocene marls and turbidites. It implied 3?km of displacement of the Monte Perdido thrust unit with respect to the underlying Gavarnie unit. In this area the cleavage development by pressure-solution is linked to the Monte Perdido and Gavarnie thrust activity. The core zone of the fault, about 6?m thick, consists of an interval of intensely deformed clay-bearing rocks bounded by major shear surfaces. The deformed sediment is markedly darker than the protolith. Calcite-quartz shear veins along the shear planes are abundant. Detailed SEM and TEM observations of highly deformed fault zone samples indicate that clay mineral enrichment in the core zone of the fault is not only related to passive increase by pressure-solution mechanism but that dissolution?Crecrystallization of phyllosilicates occurs during deformation. A mineral segregation is observed in the highly deformed zone. Newly formed 2M ₁ muscovite is present along the cleavage whereas IIb chlorite crystals fill S_V2 shear veins suggesting syntectonic growth of phyllosilicates in the presence of fluids in low-grade metamorphic conditions. These mineralogical reactions act as weakening processes and would favour Monte Perdido fault creeping.     

Evidence for syntectonic crystallization for the mudstone to slate transition at Lehigh gap,Pennsylvania, U.S.A.

Data primarily for phyllosilicates have been obtained for the continuous transitional sequence from mudstone to slate with well-developed slaty cleavage at Lehigh Gap, Pennsylvania, and for slates from quarries in the same area. Samples were studied by optical microscopy, powder X-ray diffraction and electron microprobe analysis, with emphasis on transmission and analytical electron microscopy. Mineral grains are virtually free of deformation-induced strain. Concomitant with the gradual development of cleavage normal to bedding the following changes are observed or confirmed: (1) the orientation of phyllosilicate grains changes discontinuously from being preferentially parallel to bedding to being parallel to cleavage; (2) crystal imperfections as expressed in layer terminations, low angle grain boundary-like features and other defects decrease in density; (3) complex mixed layering is replaced by homogeneous packets of layers of single phases and (4) illite transforms to muscovite, with increase in K + Al and change from a 1M_d to 2M polytype. Slaty cleavage apparently develops due in part to pressure solution of phyllosilicates oriented parallel to bedding, mass transport of components, and crystallization to form new grains parallel to cleavage. It reflects transitions from imperfect, metastable phases toward ordered stable phases in a low temperature (∼225°C) metamorphic environment.     

Very Low Grade Metamorphism of Upper Paleozoic–Lower Mesozoic Sedimentary Rocks Related to Burial and Thrusting in the Central Taurus Belt,Konya, Turkey

Metasedimentary and sedimentary rocks that represent the allochthonous Bolkardagi Unit crop out in the Central Taurus Belt. Devonian units include mainly slate, metadolomite, metadolomitic limestone, and metasandstone. Slates with slaty cleavage and chlorite-mica stacks are characterized by phyllosilicate, quartz, calcite, dolomite, feldspar, and goethite. Phyllosilicates consist of 2M₁ and lesser amounts of 1M muscovite, IIb chlorite, pyrophyllite, paragonite. PM, C-V, C-S. rectorite, and dickite, and reflect conditions of the low epizone-anchizone. In the Carboniferous-Triassic units, limestone, clayey limestone, dolomitic limestone, marl, shale, and sandstone retaining primary textures are composed of calcite, dolomite, quartz,1Md illite, chlorite, and I-S, and locally smaller quantities of 2M₁ muscovite, PM, paragonite, pyrophyllite, and rectorite. In contrast, the Triassic formation is made up of calcite, 1M_d illite, I-S, kaolinite, smectite, chlorite, C-S, C-V, dolomite, and quartz. Textural and mineralogical data indicate that development of the diagenetic-metamorphic grade in the Central Taurus was related to sedimentary burial and thrusting; moreover, the metasedimentary rocks were metamorphosed in a typical anticlockwise P-T-t pathway in an extensional setting.     

Grain growth and re-orientation of phyllosilicate minerals during the development of slaty cleavage in the South Kitakami Mountains,northeast Japan

Using X-ray diffraction analysis, the mutual relations among illite crystallinity, degree of preferred orientation of chlorite, grain size change of chlorite and illite during metamorphism and development of slaty cleavage have been investigated for argillaceous rocks in the South Kitakami Mountains, northeast Japan.The metamorphic grade of IC (illite crystallinity index) = 0.29 is a critical one, beyond which the homogenization of chlorite composition, coarsening of chlorite and illite grains and degree of preferred orientation of chlorite are abruptly advanced. Grain coarsening is also promoted by the development of slaty cleavage, especially in the range of coarser grain size.The oriented growth by the effects of both the anisotropy of intrinsic growth rate of mineral grains and that of the environment in which grains grow, is considered to bring about the preferred orientation of chlorite and illite.     

Climatic and tectonic uplift evolution since ~7 Ma in Gyirong basin, southwestern Tibet plateau: clay mineral evidence

Climate evolution associated with the uplift in Gyirong, southern margin of the Tibetan plateau, was investigated based on the clay mineralogy of the Gyirong sediments, using X-ray diffraction and scanning electron microscopy methods. The (chlorite + illite)/(kaolinite + smectite) ratio and the illite crystallinity index suggest the trend of paleoclimate evolution in Gyirong basin during ~7–1.7 Ma BP, with a warm and humid climate in ~7.0–5.8 Ma, a relative cool and dry climate in ~5.8–5.5 Ma, a relative warm and humid climate in ~5.5–2.5 Ma, and a much warmer climate in ~2.5–1.7 Ma, respectively. The fluctuating kaolinite/smectite index and calcite content and the frequent occurrence of gypsum in the episode of ~6.7–5.5 Ma suggest intense climatic fluctuations between humid and more seasonal humid conditions. Five peaks exhibit at 5.8, 4.9, 4.3, 3.6, and 2.5 Ma in the curves of illite and chlorite content and illite crystallinity. The intense uplift and tectonic-forced cooling at ~5.8 and 4.3 Ma were indicated by the high-illite crystallinity index and illite and chlorite content. A remarkable increase in illite and chlorite content associated with only little increase in illite crystallinity at ~3.6 Ma indicates a rapid uplift, but no significant climate change. And a sharp increase in illite crystallinity, while small change in illite and chlorite content at ~2.5 Ma suggests that no remarkable relief was produced by the uplift, which may take place in the whole south Tibet plateau, while cooling at 4.9 Ma is probably a record of the global climate cooling.     

可可西里盐湖表层沉积物中粘土矿物的环境信息

通过对可可西里盐湖表层沉积物中粘土矿物的研究,以期获得近年来湖区的某些环境信息.研究结果表明:沉积物中的粘土矿物主要为伊利石和绿泥石,非粘土矿物主要为石英、方解石和长石以及少量白云石、文石、闪石和石膏等.样品中＜2μm的粘土矿物以伊利石和绿泥石为主,局部样品含少量有序伊/蒙混层.根据样品分布特点和粘土矿物的组合类型,将样品划分为3个区域:1区和3区的矿物组合为伊利石、绿泥石和有序伊/蒙混层;2区为伊利石和绿泥石,无伊像混层矿物.其中1区和3区样品的结晶度(IC)范围为0.41～0.59,均值为0.51;2区样品的结晶度范围为0.25～0.40,均值为0.34,明显低于1区和3区,说明2区样品中的伊利石具有更高的结晶度.样品的伊利石化学指数(CI)均小于0.5,表明该伊利石为富Fe-Mg伊利石,主要是物理风化作用的结果.伊利石和绿泥石作为主要粘土矿物反映了近年来整个湖区的环境以干冷为主,局部区域(1区和3区)出现的少量有序I/S混层矿物则指示在短期内曾经历过短暂的干湿交替环境.此外,在酸性介质条件下,少量伊利石发生弱水解作用导致晶格中的K+淋失,并转化为伊/蒙混层矿物,同时也降低了伊利石的结晶度.     

K-feldspar rich shales from Jurassic bedded cherts in southeastern Slovenia

The study area in southeastern Slovenia is part of the transitional zone between the internal and the external Dinarides. Within Jurassic bedded cherts there are up to 2 cm thick shale intercalations, consisting of laminated, soft, fine-grained, green to brown material whose origin has been in question. In the majority of Tethyan cherts, the interbedded material is reported to be volcanogenic and/or terrigenous, although a detailed mineralogical analysis of the material is lacking. An XRD analysis confirmed the presence of quartz, illite, chlorite and K-feldspar, which is the prevailing component in some samples. Major and trace element data exclude both a volcanogenic and an hydrothermal origin. Several discrimination diagrams indicate the upper crustal terrigenous nature of shales and a biogenic silica source. The source material was probably from a Variscan crust, which at the time of deposition had already been weathered to kaolinite, and some sporadic muscovite. The MnO/Al₂O₃ ratio suggests a slow sedimentation rate of cherts and a faster one for shales, which probably settled from distal turbidity currents. The negative Ce anomaly indicates prolonged contact with ocean water. Sediments were deposited on a Tethyan passive margin, originally as silica-rich carbonate beds intercalated with mud. During late diagenesis, the mixing of marine and meteoric waters caused the further silicification of limestone and simultaneous potassium enrichment of shale which led to their alteration into illite or chlorite and, in sediments already rich in K-minerals, into K-feldspar.     

Chlorite crystallinity: an empirical approach and correlation with illite crystallinity, coal rank and mineral facies as exemplified by Palaeozoic and Mesozoic rocks of northeast Hungary

Abstract Fairly strong (r= 0.75–0.85) positive linear correlations were found between crystallinity indices (peak widths) measured on the first two basal reflections of chlorite and those of illite–muscovite in <2-μm fractions of a representative shale–slate–phyllite series from Palaeozoic and Mesozoic formations of northeast Hungary. The metamorphic grade ranges from late or deep diagenesis through anchizone to epizone conditions. Chlorite crystallinity values measured on air-dried and ethylene-glycol-solvated samples suggest that the effects of expandable interlayers are negligable, especially in the higher grade (～temperature) part of the series. However, the greater scattering of crystallinity values for the chlorite 001 reflection compared to those of the 002 reflection may be related to the effects of minor amounts of interlayered and/or discrete smectite and/or vermiculite. With increasing metamorphic grade and advancing equilibrium recrystallization, the chlorite compositions in different samples become more homogenous. No correlation exists between crystallinity and changes in chlorite composition as estimated from the intensity ratios of basal reflections. Hence an increase of domain size and a decrease of lattice distortion with increasing grade (～temperature) may be decisive factors affecting chlorite crystallinity. Chlorite crystallinity can be applied as a reliable regional, statistical technique complementary with, or instead of, the illite crystallinity method. The illite and chlorite crystallinity scales used here are related to Kübler's epi-, anchi- and diagenetic zones and correlated with coal rank, conodont colour alteration and mineral facies data. As the effects of the detrital white mica can be observed even in the <2-μm fractions of anchizonal metapelites, the anchizone boundaries determined solely on the base of ‘fixed’illite crystallinity values may vary with amounts of detrital and newly formed muscovite–illite. Hence a complex approach utilizing more than one method for determination of grade is preferred for petrogenetic purposes, even if relationships between crystallinity scales, coal rank and mineral facies also vary strongly in different tectonic settings and lithologies.     

Alteration of the Callovo–Oxfordian clay from Meuse-Haute Marne underground laboratory (France) by alkaline solution. I. A XRD and CEC study

The reaction of the clay fraction of the Callovo–Oxfordian hard shale formation hosting the French underground laboratory site, with high pH NaOH, KOH and Ca(OH)₂ solutions has been investigated through closed system experiments at 60, 90 and 120 °C over 6, 24 and 168 h. The mineralogical composition of the run samples has been determined using X-ray diffraction (XRD) of randomly oriented powders showing the formation of different species of zeolites (analcime, chabazite, phillipsite) and Ca silicates (tobermorite, katoite). The phyllosilicates were studied using XRD of oriented preparations and cation exchange capacity measurements. Detrital or diagenetic mica and chlorite in the <2 μm fraction remain unchanged. On the contrary, the smectite and random illite–smectite mixed layer minerals are strongly reactive. The expandable layers of montmorillonite type are selectively dissolved while beidellitic ones survive or are transitionally formed.