Reaction progress in chloritic material: an electron microbeam study of the Taveyanne greywacke, Switzerland

Chlorite and associated minerals from the volcanogenic Taveyanne metasediment of the western Helvetic nappes, Switzerland, were investigated by electron microprobe (EMP) and transmission electron microscopy (TEM) in order to determine their textural and chemical evolution during low-temperature metamorphism. EMP analyses of chloritic material from sub-greenschist facies outcrops show a decrease of Si and Σ(Ca, Na, K) with increasing metamorphic grade. A number of conclusions may be drawn from combined TEM images and analytical electron microscopy (AEM) data. 1 In diagenetic-grade samples, chlorite crystals (observed maximum defect-free distance=80 nm) always contain some 1 nm layers (with a maximum of 29% of all layers) and less frequently some 0.7 nm berthierine-like layers. With increasing grade, the amounts of 1 and 0.7 nm layers decrease, and most chlorite from the epizone is structurally pure or contains less than 2% of 1 nm layers. 2 A positive correlation was found between the amount of 1 nm layers and the Ca+K+Na content, indicating that the 1 nm layers are saponite. 3 Observations and calculations suggest that the transformation reaction of saponite to chlorite takes place by the replacement of the interlayer cations in saponite by brucite-like layers resulting in a local volume decrease. In contrast, the destruction of berthierine has only minor influence on the local bulk volume. These results confirm recent studies which show that the change in composition measured by EMP of diagenetic-grade chloritic material are mainly the result of mixtures of chlorite and saponite. The use of chlorite ‘geothermometry’ in such systems is greatly influenced by the presence of saponite and hence is not based on reaction equilibria, even though temperatures calculated in this study agree with temperatures derived from other methods. Therefore, chlorite evolution should be treated as a kinetically controlled grade indicator and developed as a qualitative scale similar to the illite crystallinity index.     

Polysomatism,polytypism, defect microstructures,and reaction mechanisms in regularly and randomly interstratified serpentine and chlorite

High-resolution (HRTEM) and analytical electron (AEM) microscopic evidence for a polysomatic series based on regular interstratifications of serpentine (amesite) and chlorite (clinochlore) are reported from an altered skarn in Irian Jaya. The assemblage includes regular interstratifications of one clinochlore and two (2:1; three structural variants), three (3:1), and four (4:1) amesite composition 1:1 layers as well as randomly interstratified serpentine and chlorite. The order of abundance of regularly interstratified minerals is 1:1>2:1>4:1>3:1. Atomic-resolution images, image simulations, and comparison between calculated and observed diffracted intensities verify the proposed 1:1 and 2:1 structures and reveal details of their defect microstructures. AEM data show that compositions are linear combinations of the associated amesite and clinochlore. The 1:1, 2:1, 3:1, and 4:1 minerals occur both as discrete sub-micron crystals and as domains within serpentine or chlorite. Some crystals of the 2:1 phase were sufficiently large for study by X-ray precession and powder methods. Crystals of the regularly interstratified 2:1, 3:1, and 4:1 phases are usually bent. High-resolution images reveal that, within polygonal segments, the layers commonly exhibit a few degrees of curvature with segments separated by antigorite-type offsets. Deformed chlorite crystals are probably replaced by interstratified minerals during an aluminum metasomatic event. Al may have been deposited from sulfuric acid-rich solutions when they interacted with calcite and dolomite to form the anhydrite-rich corona around the phyllosilicate-rich region of the core. The interstratified chlorite (clinochlore composition) suggests aluminum addition by selective conversion of a sub-set of the chlorite layers to amesite. Defect microstructures suggest that crystals of regularly interstratified material grew by direct structural modification of preexisting chlorite. Regular interstratifications may form in response to thermally controlled limits on Al solubility in chlorite and heterogeneities in the distribution of Al-rich solutions during metasomatism. Regularly interstratified minerals coexist with randomly interstratified serpentine/chlorite, chrysotile, antigorite, lizardite, and several amesite and chlorite polytypes. Tentative chlorite and amesite identifications include one-layer (b=97°, probably IIbb), one-layer (b=90, possibly Ibb), two-, and three-layer chlorites, and 2H₁ (but possibly 1M or 1T), rhombohedral (3R or 6R), and twelve-layer (Tc; non standard) serpentine polytypes. The complex phyllosilicates attest to rampant chemical and structural disequilibrium.     

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.     

Pre-ore hydrothermal alteration in an unconformity-type uranium deposit

 Hydrothermal alteration associated with the formation of unconformity-type uranium deposits is manifested mainly by intense chloritic replacement of metamorphic mineral assemblages. At the Koongarra deposit (northern Australia), three stages of pre-ore alteration were identified in chloritized metamorphic muscovite using optical microscopy, the electron microprobe, and transmission and analytical electron microscopy (TEM and AEM). During the first stage metamorphic muscovite was altered to a mica with very low interlayer occupancy (K content as low as 0.35 compared to 1 for ideal muscovite), high octahedral cation content (up to 2.3 whereas ideal muscovite has 2) and high Si content. High resolution TEM images show that these changes in composition were accompanied by frequent layer terminations in contrast to the metamorphic muscovite, whereas selected area electron diffraction patterns indicate that the altered muscovite remained a two-layer polytype. The alteration of muscovite appears more extensive in the outer alteration halo and has been almost completely eradicated in the ore zone where chloritization is more complete. During the second stage of the pre-ore alteration the altered muscovite was replaced by Mg-rich serpentine (lizardite) and clinochlore. High resolution TEM images show two 10 A˚ mica layers coalescing to one 14 A˚ chlorite layer. This type of coalescence appears to involve transformation of one dioctahedral layer of the mica structure to one trioctahedral brucite layer in the chlorite structure through dissolution of the tetrahedral sheets and cation influx in the octahedral site. The final stage of the pre-ore alteration resulted in replacement of lizardite and clinochlore by Fe-rich chlorite. Comparison of the alteration observed in metamorphic muscovite with the alteration observed in metamorphic biotite and garnet shows clearly that chloritization of these phases was also a pre-ore alteration event. Pre-ore alteration was principally characterized by the evolution of chlorite from a Mg-rich phase to an Fe-rich one. Received: 29 July 1994/Accepted: 8 January 1995     

Comparison of diagenetic and low-grade metamorphic evolution of chlorite in associated metapelites and metabasites: an integrated TEM and XRD study

Chlorite is a common sheet silicate that occurs in various lithologies over a wide grade range involving diagenesis and low‐grade metamorphism. Thus, the reaction progress of chlorite offers a unique opportunity for direct correlation of zonal classification of metasedimentary rocks based on illite crystallinity with metabasite mineral facies. To provide such correlation, chlorite crystallinity indices, apparent mean crystallite sizes and lattice strains, crystallite size distributions and compositions of chlorite from coexisting metapelites and metabasites were determined by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), analytical electron microscopy (AEM) and electron microprobe (EMP) methods. Samples were from Palaeozoic and Mesozoic formations of the Bükkium (innermost Western Carpathians, Hungary) that underwent Alpine (Cretaceous) orogenic metamorphism. Metapelites range in grade from late diagenesis to epizone, whereas metabasites vary from prehnite–pumpellyite through pumpellyite–actinolite to greenschist facies. Despite significant differences in composition, mineral assemblages and textures, reaction progress, as measured in part by chlorite crystallinity, in metapelites paralleled that in metabasites. Chlorite crystallinity and mean crystallite size increase and the proportion of mixed layers in chlorite decreases, whereas the calculated lattice strain does not change significantly with increasing metamorphic grade. Similar trends, but (especially at higher grades) significant differences, were found in mean crystallite size values using various methods for XRD line profile analyses. The increase in crystallite size with increasing grade was demonstrated also by direct TEM measurements on ion‐milled whole‐rock samples, but with a larger scatter of data at higher grades. In spite of the different kinds of mixed layering in chlorite (Mg‐rich smectitic, mostly random, local corrensite‐like units in metabasites, and Fe‐rich berthierine and dioctahedral smectite in metapelites), XRD‐calculated and TEM‐measured parameters were found to be reliable tools for measuring reaction progress and metamorphic grade of the same degree in both lithotypes.     

Phlogopite-chlorite reaction mechanisms and physical conditions during retrograde reactions in the Marble Formation,Franklin, New Jersey

A retrograde assemblage in a specimen from the Franklin Marble Formation containing an unusual occurrence of three micas has been studied. Microprobe analyses of the margarite, muscovite and phlogopite reveal significant sodium and fluorine but otherwise show little mutual solid solution. The conditions that prevailed during the retrogression estimated from phase equilibria are T=370–450° C and =0.03–0.3 at an assumed pressure of 2 kb.Examination of the phlogopite by TEM revealed replacement of phlogopite by chlorite. The chlorite occurred as small packets of layers interlayered with phlogopite. AEM analyses revealed that the chlorite composition approximates that of clinochlore. Transformations from a single phlogopite layer to one chlorite layer (a 11 reaction) and also from two phlogopite layers to one chlorite layer (a 21 reaction) have been observed. Both reactions result in a large volume change causing local strain at transition fronts. An apparently strain-free, volume-preserving transformation of 14 phlogopite layers terminating against 10 chlorite layers was observed which indicates that pervasive replacement may occur through a combination of both reactions. Topological and site occupancy changes during the transformation suggest that the reaction involves not only gain and loss of layer units, but also considerable local rupturing and reformation of bonds, concomitant with ion diffusion and interchange. Dislocations (layer terminations) at the transition front imply the existence of pathways for the fluid flow and ion transport required for mass balance.Contribution No. 397 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan, USA     

Contribution of long-term hydrothermal experiments for understanding the smectite-to-chlorite conversion in geological environments

The smectite-to-chlorite conversion is investigated through long-duration experiments (up to 9 years) conducted at 300 °C. The starting products were the Wyoming bentonite MX80 (79 % smectite), metallic iron and magnetite in contact with a Na–Ca chloride solution. The predominant minerals in the run products were an iron-rich chlorite (chamosite like) and interstratified clays interpreted to be chlorite/smectite and/or corrensite/smectite, accompanied by euhedral crystals of quartz, albite and zeolite. The formation of pure corrensite was not observed in the long-duration experiments. The conversion of smectite into chlorite over time appears to take place in several steps and through several successive mechanisms: a solid-state transformation, significant dissolution of the smectite and direct precipitation from the solution, which is over-saturated with respect to chlorite, allowing the formation of a chamosite-like mineral. The reaction mechanisms are confirmed by X-ray patterns and data obtained on the experimental solutions (pH, contents of Si, Mg, Na and Ca). Because of the availability of some nutrients in the solution, total dissolution of the starting smectite does not lead to 100 % crystallization of chlorite but to a mixture of two dominant clays: chamosite and interstratified chlorite/smectite and/or corrensite/smectite poor in smectite. The role of Fe/(Fe + Mg) in the experimental medium is highlighted by chemical data obtained on newly formed clay particles alongside previously published data. The newly formed iron-rich chlorite has the same composition as that predicted by the geothermometer for diagenetic to low-grade metamorphic conditions, and the quartz + Fe-chlorite + albite experimental assemblage in the 9-year experiment is close to that fixed by water–rock equilibrium.     

Microstructures and compositional variation in the intravolcanic bole clays from the eastern Deccan volcanic province: Palaeoenvironmental implications and duration of volcanism

Clay minerals associated with intra-volcanic bole horizons of varied colours and thicknesses contain montmorillonite, halloysite and kaolinite, show distinct microstructures and microaggregates. In kaolinite, Fe³⁺ ions substitute for Al³⁺ at octahedral sites. Most of these clays are dioctahedral type, show balance between net layer and interlayer charges. The interstratified illite — smectite (I/S) mixed layers containing variable proportions of montmorillonite. Illite contains sheet-like, well oriented microaggregates. The parallel stacks of chlorite sheets show chlorite/smectite (C/S) mixed layers. Progressive enrichment of Fe and depletion of Al ions with the advancement of kaolinization process is observed. High order of structural and compositional maturity observed in these bole clays, indicate long hiatus between the two volcanic episodes.     

Reaction pathways and reaction progress for the smectite-to-chlorite transformation: evidence from hydrothermally altered metabasites

The transformation from smectite to chlorite has been interpreted as involving either a disequilibrium chlorite/smectite mixed‐layering sequence, or an equilibrated discontinuous sequence involving smectite–corrensite–chlorite. Here, analysis of the smectite to chlorite transition in different geothermal systems leads us to propose that the transformation proceeds via three contrasting reaction pathways involving (i) a continuous mixed‐layer chlorite/smectite series; (ii) a discontinuous smectite–corrensite–chlorite series and (iii) a direct smectite to chlorite transition. Such contrasting pathways are not in accord with an equilibrium mineral reaction series, suggesting that these pathways record kinetically controlled reaction progress. In the geothermal systems reviewed the style of reaction pathway and degree of reaction progress is closely correlated with intensity of recrystallization, and not to differences in thermal gradients or clay grain size. This suggests a kinetic effect linked to variation in fluid/rock ratios and/or a contrast between advective or diffusive fluid transport. The mode of fluid transport provides a means by which the rates of dissolution/nucleation/growth can control the reaction style and the reaction progress of the smectite to chlorite transition. Slow rates of growth are linked to the first reaction pathway involving mixed‐layering, while increasing rates of growth, relative to nucleation, promote the generation of more ordered structures and ultimately lead to the direct smectite to chlorite transition, representative of the third pathway.     

The smectite–chlorite transition in drillhole NJ-15, Nesjavellir geothermal field, Iceland: XRD, BSE and electron microprobe investigations

Abstract In well NJ-15 of the Nesjavellir geothermal field, Iceland, the transition of discrete smectite into discrete chlorite has been studied from drill cuttings recovered at depths of less than 1714 m and over a continuous range of temperatures between 60 and 300° C. At temperatures below 180° C, the clay fractions contain mixtures of di- and trioctahedral smectites, whose layer charge increases with depth. Between 200 and 240° C, discrete smectites have transformed into smectite-rich, randomly interstratified chlorite and smecite ( R 0 C/S). Because the abundance of chlorite interlayers in this C/S is generally <20%, its presence can be detected only by electron microprobe techniques and not by X-ray diffraction. Between 245 and 265° C, both regularly ( R 1) and randomly interstratified C/S are the predominant layer silicates. Discrete chlorite first appears at approximately 270° C and coexists with minor amounts of R 0 C/S at higher temperatures.
R 0 and R 1 C/S form a nearly complete compositional series between trioctahedral saponite and discrete chlorite end-members. The interlayer cation and Si content of smectites and C/S decrease with increasing temperature. The Mg/(Mg + Fe) content of smectite, C/S, and chlorite is unrelated to temperature. The percentage of chlorite in C/S, as determined by electron microprobe analyses, increases continuously with increasing temperature, except for occurrences of smectite-rich C/S in fresh basaltic dykes which have not thermally equilibrated with the higher grade country rocks.     

Chlorite-illite/muscovite interlayered and interstratified crystals: A TEM/STEM study

Phyllosilicates in rocks which are transitional from mudstone to slate from Lehigh Gap, Pa., have been studied by a variety of techniques, including high resolution Transmission Electron Microscopy and Analytical Electron Microscopy. The principal minerals are white mica which is transitional from illite in mudstone to ordered twolayer mica in slate, and chlorite. 7Å berthierine occurs more rarely. Dioctahedral and trioctahedral layers are shown to be interleaved in individual crystals at all scales between the following two end members: (1) both random and regular 11 interlayering at the scale of individual layers, as shown, in part, by lattice fringe images. (2) packets of trioctahedral and dioctahedral layers up to a few thousand Ångstroms or microns in thickness, detectable with ordinary optical techniques. The complete range of intermediate structures is represented in samples which are in transition to slate. Bulk analytical (EMPA), X-ray diffraction or other measurements are shown to result in averages over both kinds of layers when TEM techniques are not used.Contribution No. 400 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan     

Illite/smectite transformation in detrital glaucony during burial diagenesis of sandstone: A study from Siri Canyon – Danish North Sea

Detrital glaucony in the Palaeogene glauconitic sandstones in Siri Canyon, Danish North Sea, has been analysed from 15 exploration wells by X‐ray diffraction, electron microprobe and scanning electron microscopy. These sandstones consist of mixed‐layer illite/smectite and have a large variability in chemical composition and structure. In the most shallow wells (ca 1700 m), the glaucony is rich in Fe and consists of mixed‐layer illite/smectite with random‐interstratification (R = 0). In the depth interval from 1700 to 2000 m, the composition changes as Si is incorporated. The structure changes to ordered R = 1. Further increase in burial leads to the loss of Fe. Ordered R = 3 mixed‐layer illite/smectite is recognized from burial depths of 2200 m. The proportion of illite in illite/smectite mixed layers increases only slightly with depth and temperature. Although the structural changes generally are associated with chemical changes, they can also take place isochemically when the detrital glaucony is tightly embedded in earlier cement, which prevented chemical exchange. The glaucony transformation in the Siri Canyon sandstones partly reflects a supply of Si and partly significant loss of Fe. Thus, the glaucony transformation relates to the general diagenesis of the host sandstone. These sandstones are cemented by microquartz at an early stage, followed by precipitation of Fe‐rich grain‐coating berthierine or chlorite.     

Chlorite dissolution in the acid ph-range: a combined microscopic and macroscopic approach

The dissolution of chlorite with intermediate Fe-content was studied macroscopically via mixed flow experiments as well as microscopically via atomic force microscopy (AFM). BET surface area normalized steady state dissolution rates at 25 °C for pH 2 to 5 vary between 10⁻¹² and 10⁻¹³ mol/m^2.s. The order of the dissolution reaction with respect to protons was calculated to be about 0.29. For pH 2 to 4, chlorite was found to dissolve non-stoichiometrically, with a preferred release of the octahedrally coordinated cations. The additional release of octahedrally coordinated cations may be due to the transformation of chlorite to interstratified chlorite/vermiculite from the grain edges inward.In-situ atomic force microscopy performed on the basal surfaces of a chlorite sample, which has been preconditioned at pH 2 for several months, indicated a defect controlled dissolution mechanism. Molecular steps with height differences which correspond to the different subunits of chlorite, e.g. TOT sheet and brucite like layer, originated at surface defects such or compositional inhomogenities or cracks, which may be due to the deformation history of the chlorite sample. In contrast to other sheet silicates, at pH 2 nanoscale etch pits occur on the chlorite basal surfaces within flat terraces terminated by a TOT-sheet as well as within the brucite like layer. The chlorite basal surface dissolves layer by layer, because most of the surface defects are only expressed through single TOT or brucite-like layers. The defect controlled dissolution mechanism favours dissolution of molecular steps on the basal surfaces compared to dissolution of the grain edges. At pH 2 the dissolution of the chlorite basal surface is dominated by the retreat of 14 Å steps, representing one chlorite unit cell.The macroscopic and microscopic chlorite dissolution rates can be linked via the reactive surface area as identified by AFM. The reactive surface area with respect to dissolution consists of only 0.2% of the BET-surface area. A dissolution rate of 2.5 × 10⁻⁹ mol/m²s was calculated from macroscopic and microscopic dissolution experiments at pH 2, when normalized to the reactive surface area.     

Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al_0.975FeIII_0.182FeII_1.422Mg_0.157Li_0.035Mn_0.002)(Si_1.332Al_0.668)O₅(OH)₄] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si_2.633Al_1.367)(Al_1.116FeIII_0.215Mg_2.952FeII_1.712Mn_0.012Ca_0.011)O₁₀(OH)₈]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.     

层状硅酸盐矿物晶体结构的多体性组装模式与构筑原理

将层状硅酸盐矿物晶体结构中属性不同的二维结构单元体看成是不同的结晶学模块,研究了一般层状硅酸盐矿物和间层矿物的多体性组装模式和构筑原理。结果表明,不同二维结构单元体(包括硅氧四面体片、八面体片、层间域(物))的构筑基本符合球体紧密堆积原理,紧密堆积层平行{0001};四面体片与八面体片构筑TO和TOT结构层时采取多种机制消除二者在二维尺寸上的差异;两种模式的结构层与不同类型的层间物(域)组装形成六种组装模式的晶层;并通过二维结构单元体的组合规律的分析,计算出可能存在的28种TOT型间层结构,它们分属于6种间层结构多体性组装模式;间层结构中,结构层对于八面体片是不对称的,并在属性上表现出极性特征;间层矿物的晶层类型可用6种多体性组装模式加以表达。层状硅酸盐矿物结构的多体性分析与组装模式的研究,对于矿物晶体化学研究是非常重要的。     

我国二八面体绿泥石的发现及其混层矿物的研究

绿泥石作为重要的粘土矿物已被广泛研究。然而,多数属于三八面体亚群。自从α-绿泥石、端铅绿泥石(Nagolnit)以及片硅铝石(donbassite)发现以后,才开始确认二八面体绿泥石的存在。     

间层矿物的结构参数与分类探讨

从间层的概念出发，对四个间层结构参数的定义和意义进行总结，并根据间层矿物的结构和组成对其进行了分类探讨。首先根据晶层种类将间层矿物分为同类结构基元间层矿物和异类结构基元间层矿物两大类，然后根据变差系数划分出规则间层矿物和不规则间层矿物，最后根据间层比、连接概率等特征划分出有序间层、无序间层和带状间层。     

Burial Metamorphism of the Ordos Basin in Northern Shaanxi

Burial metamorphism has been found in the Ordos basin of northern Shaanxi. On the basis of a rather intensive study of burial metamorphism of sandstone, it has been shown that the evolution from diagenesis to metamorphism involves four stages: cementation of clay minerals, regrowth of pressolved quartz and feldspar, cementation of carbonates and formation of laumontite. On that basis it has been put forward that the laumontite is formed by burial metamorphism of clay and carbonate minerals. According to the thermodynamic data of minerals, the conditions under which laumontite is formed are T<250℃ and X_(CO_2)<0.17. High-resolution SEM and TEM studies of clay minerals in mudstone show that there occur a mixed layer assemblage of bertherine and illite/chlorite and transformation from bertherine to chlorite. On that basis coupled by the X-ray diffraction analysis the author suggests the following transformation of clay minerals during burial metamorphism: the earliest smectite-kaolinite assemblage changes into the bertherine-illite mixture with increasing depth, then into the illite/chlorite mixed layer assemblage and finally into dispersed individual illite and chlorite. The reaction of the transformation is:smectite+kaolinite+K~+=illite+chlorite+quartz According to the study of the oxygen isotope thermometry of the coexisting illitequartz pair, the temperature of the above transformation is lower than 180℃.     

Relationship of diagenetic chlorite rims to depositional facies in Lower Cretaceous reservoir sandstones of the Scotian Basin

The relationship between diagenetic chlorite rims and depositional facies in deltaic strata of the Lower Cretaceous Missisauga Formation was investigated using a combination of electron microprobe, bulk geochemistry and X‐ray diffraction data. The succession studied comprises several stacked parasequences. The delta progradational facies association includes: (i) fluvial or distributary channel sandstones (some with tidal influence); (ii) thick‐bedded delta‐front graded beds of sandstone interpreted as resulting from fluvial hyperpycnal flow during floods and storms; and (iii) more distal muddier delta‐front and prodeltaic facies. The transgressive facies association includes lag conglomerate, siderite‐cemented muddy sandstone and mudstone, and bioclastic sandy limestone. Chlorite rims are absent in the fluvial facies and best developed in thick sandstones lacking mudstone baffles. Good quality chlorite rims are well correlated with Ti in bulk geochemistry. Ti is a proxy for Fe availability, principally from the breakdown of abundant detrital ilmenite (FeTiO₃). Under conditions of sea floor diagenesis, the abrupt decrease in sedimentation rate at transgressive surfaces caused progressive shallowing of the sulphate‐depletion level and of the overlying Eh‐controlled diagenetic zones, resulting in conditions suitable for diagenetic formation of berthierine to migrate upwards through the packet of reservoir sandstones. This early diagenetic berthierine suppressed silica cementation and later recrystallized to chlorite. Thick euhedral outer chlorite rims were precipitated from formation water in sandstone lacking muddy baffles on this chlorite substrate and inhibited late carbonate cementation. This study thus shows that the preservation of porosity by chlorite rims is a two‐stage process. Rapidly deposited delta‐front turbidite facies create early diagenetic conditions that eventually lead to the formation of chlorite rims, but the best quality chlorite rims are restricted to sandstones with high permeability during burial diagenesis.     

Deposition of talc — kerolite–smectite — smectite at seafloor hydrothermal vent fields: Evidence from mineralogical,geochemical and oxygen isotope studies

Talc, kerolite–smectite, smectite, chlorite–smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite–smectite to smectite-rich kerolite–smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite–smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite–smectite with lower crystalline perfection as the proportion of smectite layers in kerolite–smectite increases.Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite–smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250 °C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200–250 °C) phase forming deep within the sediment (～ 0.8 m). Chlorite and chlorite–smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150–200 °C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two controls on the precipitation of this sequence are the silica activity and Mg/Al ratio (i.e. the degree of mixing of seawater with hydrothermal fluid). Higher silica activity favors the formation of talc relative to tri-octahedral smectite. Vent structures and sedimentary cover preclude complete mixing of hydrothermal fluid and ambient seawater, resulting in lower Mg/Al ratios in the interior parts of the chimneys and deeper in the sediment which leads to the precipitation of phyllosilicates with lower Mg contents. Talc and kerolite–smectite have very low trace- and rare earth element contents. Some exhibit a negative or flat Eu anomaly, which suggests Eu depletion in the original hydrothermal fluid. Such Eu depletion could be caused by precipitation of anhydrite or barite (sinks for Eu²⁺) deeper in the system. REE abundances and distribution patterns indicate that chlorite and chlorite–smectite are hydrothermal alteration products of the background turbiditic sediment.