The smectite to chlorite transition in a fossil seamount hydrothermal system: the Basement Complex of La Palma, Canary Islands

Abstract The hydrothermal metamorphism of a sequence of Pliocene-aged seamount extrusive and volcanoclastic rocks on La Palma includes a relatively complete low-P-T facies series encompassing the zeolite, prehnite-pumpellyite, and greenschist facies. The observed mineral zonations imply metamorphic gradients of 200–300° C km^-1. The transition from smectite to chlorite in the La Palma seamount series is characterized by discontinuous steps between discrete smectite, corrensite and chlorite, which occur ubiquitously as vesicles and, to a much lesser extent, vein in-fillings. Trioctahedral smectites [(Mg/(Fe + Mg) = 0.4–0.75] occur with palagonite and Na-Ca zeolites such as analcime and a thompsonite/natrolite solid solution. Corrensite [(Mg/(Fe + Mg) = 0.5–0.65] first appears at stratigraphic depths closely corresponding to the disappearance of analcime and first appearance of pumpellyite. Discrete chlorite [(Mg/(Fe + Mg) = 0.4–0.6] becomes the dominant layer silicate mineral coincident with the appearance of epidote and andraditic garnet. Within the stratigraphic section there is some overlap in the distribution of the three discrete layer silicate phases, although random interstratifications of these phases have not been observed. Although smectite occurs as both low- and high-charge forms, the La Palma corrensite is a compositionally restricted, 1:1 mixture of low-charge, trioctahedral smectite and chlorite. Electron microprobe analyses of coarse-grained corrensite yield structural formulae close to ideal values based on 50 negative charge recalculations. Calcium (average 0.20 cations/formula unit) is the dominant interlayer cation, with lesser Mg, K and Na. The absence of randomly interlayered chlorite/smectite in the La Palma seamount series may reflect high, time-integrated fluid fluxes through the seamount sequence. This is consistent with the ubiquity of high-variance metamorphic mineral assemblages and the general absence of relict igneous minerals in these samples.     

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.     

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.     

Mineral chemistry of clays associated with the Jhilmili intertrappean bed in the eastern Deccan volcanic province: Palaeoenvironmental inferences and KTB transition

Jhilmili intertrappean bed (～13 m thick) attains its significance with the recent discovery of brackish water ostrocod and planktonic foraminifera fossils (Keller et al. 2009; Khosala et al. 2009). Present XRD data revealed abundance of montmorillonite > montmorillonite/chlorite mixed layer > palygorskite in five physically distinct lithounits namely: (a) lower chocolate brown siltstone with green patches, followed by (b) brick red clayey siltstone, (c) greenish grey clay, (d) yellowish brown clay and (e) uppermost olive grey to dark brown silt layers in the successionrepresent higher weathering indices and annual precipitation, reflecting cyclic, but longer spells of weathering. Occurrence of M/C mixed layer with the smectite in Jhilmili area is suggestive of their derivation from the later, whilst montmorillonite to palygorskite transformation is ascribed to the drastic changes in the humid to arid climate, where former served as a source of Al and some of the Si and Mg ions for the later. Jhilmili and Anjar clays represent similar charge occupancies at different sites, but later contains relatively higher amount of palygorskite, formed in the arid environment. Majority of the trace elemental data plots for Jhilmili clays lie within the upper and lower limits of infra (Lametas)-/inter-trappeans clays. The continuous release of Cu throughout the succession (mainly in the palygorskite dominated clays) indicates oxidizing conditions. PAAS normalized REE data plots for these clays show progressive enrichment in the HREE contents in the lower part, but, upper part of the succession is marked by positive cerium anomaly, reflecting oxidizing conditions prevailed at the later stage of the succession. These conditions continued, but, were not conducive to HREE enrichment as evidenced by their depletion in the upper part of the succession. The Ce anomaly observed in the middle part of the succession is similar to that form by continental weathering of the basalt, ascribed to Ce precipitation in the oxic environment, thus suggestive of drastic changes in the oxidizing conditions. Thermodynamic data-sets for Jhilmili clays show I/S mixed layer and celadonite compositions, whereas, Jabalpur infra-/inter-trappean clays correspond to Mg smectites and celadonite end members, thus, representing compositional commonality with those of the other clays derived from the continental weathering of basalt protolith. Jhilmili smectites and smectite-chlorite mixtures show compositional similarity with the dioctahedral and trioctahedral smectites and the smectites formed at 250°C, having compositions between trioctahedral smectite and chlorite, thus, assigning high temperatures for their formation, where the heat required for the formation of these clays was possibly derived from the hydrothermal fluids, associated with the Deccan volcanism.     

Integrated TEM, XRD and electron microprobe investigation of mixed-layer chlorite–smectite from the Point Sal ophiolite, California

Abstract Five basalt samples from the Point Sal ophiolite, California, were examined using HRTEM and AEM in order to compare observations with interpretations of XRD patterns and microprobe analyses. XRD data from ethylene-glycol-saturated samples indicate the following percentages of chlorite in mixed-layer chlorite–smectite identified for each specimen: (i) L2036 ± 50%, (ii) L2035 ± 70 and 20%, (iii) 1A-13 ± 70%, (iv) 1B-42 ± 70%, and (v) 1B-55 = 100%. Detailed electron microprobe analyses show that 'chlorite'analyses with high Si, K, Na and Ca contents are the result of interlayering with smectite-like layers. The Fe/(Fe + Mg) ratios of mixed-layer phyllosilicates from Point Sal samples are influenced by the bulk rock composition, not by the percentage of chlorite nor the structure of the phyllosilicate.
Measurements of lattice-fringe images indicate that both smectite and chlorite layers are present in the Point Sal samples in abundances similar to those predicted with XRD techniques and that regular alternation of chlorite and smectite occurs at the unit-cell scale. Both 10- and 14-Å layers were recorded with HRTEM and interpreted to be smectite and chlorite, respectively. Regular alternation of chlorite and smectite (24-Å periodicity) occurs in upper lava samples L2036 and 1A-13, and lower lava sample 1B-42 for as many as seven alternations per crystallite with local layer mistakes. Sample L2035 shows disordered alternation of chlorite and smectite, with juxtaposition of smectite-like layers, suggesting that randomly interlayered chlorite (<0.5)–smectite exists. Images of lower lava sample 1B-55 show predominantly 14-Å layers. Units of 24 Å tend to cluster in what may otherwise appear to be disordered mixtures, suggesting the existence of a corrensite end-member having thermodynamic significance.     

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.     

Regional retrograde alteration of sub-greenschist facies chlorite to smectite

Dioctahedral smectite is present as a retrograde alteration product of chlorite in Permian-Triassic red slates of the Malaguide Complex in Sierra de Espuña (Betic Cordillera). Mineral assemblages and textures, illite crystallinity indices, and fluid inclusion data indicate sub-greenschist facies conditions that reached at least 180°C in the higher-grade tectonic unit of the Malaguide Complex, preceding formation of smectite. Smectite, having K as the dominant interlayer cation, occurs ubiquitously intercalated with trioctahedral chlorite as thin packets of layers and as individual layers that commonly change to chlorite along layers. Although some chlorite is typically homogeneous and trioctahedral, much chlorite shows signs of alteration and has compositions corresponding to different degrees of smectite contaimination. The incompatibility of metamorphic grade with the occurrence of smectite, the general association of chlorite and smectite, and the textural relations collectively show that dioctahedral smectite is derived through replacement of trioctahedral chlorite. Such replacement occurs on a regional basis and demonstrates that caution must be used in interpreting the occurrence of smectite in pelites as being due to prograde processes. Alteration of trioctahedral chlorite under oxidizing conditions due to introduction of phreatic water after uplift of the Betic Cordillera is proposed as the cause of formation of smectite.     

Clay petrology of the Upper Triassic/Lower Jurassic terrestrial strata of the Newark Supergroup,Connecticut Valley,U.S.A.

The clay mineralogy of the Newark Supergroup (Upper Triassic/Lower Jurassic) in the Connecticut Valley was studied by X-ray diffraction analysis. Clay minerals identified in 126 samples are illite, chlorite, smectite, kaolinite, vermiculite, expandable chlorite, mixed-layer illite/smectite, mixed-layer chlorite/smectite, and mixed-layer chlorite/vermiculite. In general, the rocks are illitic with subordinate amounts of chlorite. However, the various lithofacies in the Newark Supergroup are characterized by distinct clay-mineral assemblages. Red beds of floodplain origin contain clays mainly of detrital nature with 2M illite most abundant. Subordinate amounts of chlorite, smectite, vermiculite, kaolinite and mixed-layer illite/smectite are also present. An interstratified chlorite/vermiculite occurs in red mudstone underlying basalt flows. Lacustrine gray beds are generally characterized by the clay-mineral assemblage 1Md illite + chlorite with minor amounts of smectite ane expandable chlorite. An interstratified chlorite/smectite predominates in gray mudstone associated with perennial lake cycles in the East Berlin Formation. Black shales of deeper lacustrine origin contain the assemblage 1Md ifillite + trioctahedral smectite and traces of chlorite. Illite and smectite also occur as mixed-layer phases.In many respects, the distribution of clay minerals in the Connecticut Valley can be likened to the general scheme proposed for the Permo-Triassic basins of Europe and Africa. These display both vertical and horizontal variations in clay-mineral assemblages that reflect the chemical and spatiotemporal evolution of intrabasin depositional and diagenetic environments. Chemical data indicate that magnesium, especially, was concentrated in the black muds of large perennial lakes that intermittently occupied the Connecticut rift valley. Pore waters derived from these sediments played an important role in the development of Mg-rich 2 : 1 and interstratified clay minerals during early diagenesis.     

油气储层中自生伊利石K-Ar同位素年代学研究若干问题的初步探讨

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

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。     

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.     

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.     

中国含油气盆地粘土矿物的某些矿物学特征

本文总结归纳了２０多个含油气盆地粘土矿物的类型，讨论了８种较常见的、６种较少见的和３种极少见的粘土矿物的Ｘ射线衍射特征及其成分、形态和分布等方面的矿物学特征．     

Formation of chlorite rims and the impact of pore-lining chlorite on reservoir quality: a case study from Shiqianfeng sandstones in upper Permian of Dongpu Depression,Bohai Bay Basin,eastern China

The source material, precursor and formation processes of chlorite rims, and impact of pore-lining chlorite on reservoir quality of the Shiqianfeng sandstones, Dongpu Depression, Bohai Bay Basin, China, are studied using an integrated approach, including core observation, point-count analysis of thin-sections, scanning electron microscopy, electron microprobe analysis and cathode luminescence. The petrographic analysis shows that chlorite rims consist of grain-coating chlorite, poorly crystalline pore-lining chlorite and euhedral-crystallised pore-lining chlorite. The chemical composition shows that pore-lining chlorite is mainly Fe-rich with an average of 0.785 for Fe/(Fe+Mg) ratio. Petrographic analysis shows a large amount of volcanic dust (3.0～16.0 vol%, average of 7.93 vol%) in Shiqianfeng sandstones, which determines the formation of poorly crystalline pore-lining chlorite. Transformation of volcanic dust to smectite rims started with shallow burial depth at an early diagenetic stage, followed by in situ alteration of the smectite rims to poorly crystalline chlorite rims. Euhedral-crystallised chlorite mainly develops in sandstones with high porosity, high permeability and open flow systems. Pore-lining chlorite can inhibit quartz overgrowth but cannot effectively prevent pore-filling of authigenic quartz, carbonate and kaolinite cements, and therefore cannot prevent porosity destruction. However, the occurrence of pore-lining chlorite is a barometer of good reservoir quality and intense hydrodynamic conditions.     

Hydrothermal Formation of Lath-Shaped Trioctahedral Smectite with High Crystallinity

Lath-shaped and highly crystalline trioctahedral smectites were synthesized under hydrothermal conditions. The quenched glasses with stoichiometrically dehydrated Na-smectite compositions were treated at （a） 500℃ and 100 MPa for 1 and 11 days; and （b） 300℃ and 100 MPa for 7 days. The crystallinity and particle size of products were dependent on the chemical composition of the starting glass, synthetic temperature and duration of hydrothermal treatment. The high structural ordering and large dimensions of the products were confirmed from the sharpness of XRD peaks; and hydration behavior under controlled relative humidity. Transmission electron microscopy was also performed for the characterization of the particle size of product. Particle sizes vary from ca. 10 nm to a few pm by changing the chemical compositions of the starting materials. The product with the highest structural ordering and largest dimension was obtained from Nao.33（Mg1.83Al0.67）Si4O11 glass treated at 500℃ and 100 MPa for 1 day. The obtained results also confirmed the metastability and compositional dependency in the formation of highly crystalline trioctahedral smectite at hydrothermal conditions.     

Clay Minerals in an Active Hydrothermal Field at Iheya‐North‐Knoll,Okinawa Trough

Iheya‐North‐Knoll is one of the small knolls covered with thick sediments in the Okinawa Trough back‐arc basin. At the east slope of Iheya‐North‐Knoll, nine hydrothermal vents with sulfide mounds are present. The Integrated Ocean Drilling Program (IODP) Expedition 331 studied Iheya‐North‐Knoll in September 2010. The expedition provided us with the opportunity to study clay minerals in deep sediments in Iheya‐North‐Knoll. To reveal characteristics of clay minerals in the deep sediments, samples from the drilling cores at three sites close to the most active hydrothermal vent were analyzed by X‐ray diffraction, scanning electron microscope and transmission electron microscope. The sediments are classified into Layer 0 (shallow), Layer 1 (deep), Layer 2 (deeper) and Layer 3 (deepest) on the basis of the assemblage of clay minerals. Layer 0 contains no clay minerals. Layer 1 contains smectite, kaolinite and illite/smectite mixed‐layer mineral. Layer 2 contains chlorite, corrensite and chlorite/smectite mixed‐layer mineral. Layer 3 is grouped into three sub‐layers, 3A, 3B and 3C; Sub‐layer 3A contains chlorite and illite/smectite mixed‐layer mineral, sub‐layer 3B contains chlorite/smectite and illite/smectite mixed‐layer minerals, and sub‐layer 3C contains chlorite and illite. Large amounts of di‐octahedral clay minerals such as smectite, kaolinite, illite and illite/smectite mixed‐layer mineral are found in Iheya‐North‐Knoll, which is rarely observed in hydrothermal fields in mid‐ocean ridges. Tri‐octahedral clay minerals such as chlorite, corrensite and chlorite/smectite mixed‐layer mineral in Iheya‐North‐Knoll have low Fe/(Fe + Mg) ratios compared with those in mid‐ocean ridges. In conclusion, the characteristics of clay minerals in Iheya‐North‐Knoll differ from those in mid‐ocean ridges; di‐octahedral clay minerals and Fe‐poor tri‐octahedral clay minerals occur in Iheya‐North‐Knoll but not in mid‐ocean ridges.     

Corrensite and mixed-layer chlorite/corrensite in metabasalt from northern Taiwan: TEM/AEM,EMPA, XRD,and optical studies

Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation (expandable chlorite) and/or have excess Al^VI relative to Al^IV, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and expandable chlorite, which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high Al^VI/Al^IV and low Fe^VI/(Fe+Mg)^VI ratios of chlorites are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200–500 Å thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low Al^IV/Si^IV and low Fe^VI/(Fe+Mg)^VI, while chlorite has high Al^IV/Si^IV and high Fe^VI/(Fe+Mg)^VI. This implies that the trioctahedral smectite-like component of corrensite has significantly lower Al^IV/Si^IV and Fe^VI/(Fe+Mg)^VI. The ratios of Fe^VI/(Fe+Mg)^VI and Al^IV/Si^IV thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of chlorites in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite.     

Nature of the structural and crystal-chemical heterogeneity of the Mg-rich glauconite (Riphean,Anabar Uplift)

The detailed mineralogical and structural-crystal-chemical characteristics are reported for the first time for glauconite grains extracted from the fine-platy silty-sandy dolomites at the roof of the lower subformation of the Yusmastakh Formation (Riphean, Anabar Uplift, North Siberia). Based on the complex study (X-ray diffraction, classical chemical analysis, microprobe analysis, IR-spectroscopy, thermogravimetric analysis, scanning electron microscopy with microprobe analysis, and Mössbauer spectroscopy), it was demonstrated that the studied glauconite sample is characterized by unique chemical and structural heterogeneity.The mineral structure consists of micaceous (90%), smectite (6%), and di-trioctahedral chlorite (4%) layers. Mica is classed with Al-glauconite (Al > Fe³⁺) with elevated Mg content. The elevated Mg mole fraction of the mineral is caused by the presence of Mg-bearing brucite-type interlayers of di-trioctahedral chlorite and the high Mg content in the octahedral sheets of 2: 1 layers. It was first discovered that glauconites are characterized by the heterogeneous distribution of cations over the available trans- and cis-octahedra due to the coexistence of trans- and cis-vacant octahedra and small trioctahedral clusters in octahedral sheets. The distribution of isomorphic cations over the accessible octahedral sites is also heterogeneous due to the tendency of Fe, Mg and Al, Mg cations to segregation and formation of corresponding domains.It was found that structure of the studied glauconite has a specific stacking defect: in addition to the predominant subsequent layers of similar azimuthal orientation according to 1M type (～77%), some layer fragments are rotated at 180° (～15%) and ±120° (8%). The structural-crystal-chemical heterogeneity of the mineral is explained by the fact that its microcrystals grew in the dolomitic sediment under nonequilibrium conditions of the reduction zone of a shallow-water basin with a sufficiently high content of Mg cations, which significantly contributed to the glauconite formation.     

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.     

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.