Diverse and well-preserved radiolarian assemblages were recovered from the middle Eocene sedimentary sequences drilled at Ocean Drilling Program Site 1051 (Leg 171B; western subtropical Atlantic). In addition to biostratigraphically important species, several unknown morphotypes were observed in this material, leading to the description of three new spumellarian species and 18 new nassellarian species. Described herein are: Periphaena petrushevskayae n. sp. (Phacodiscidae), Stylodictya oligodonta n. sp. (Trematodiscidae), Excentrosphaerella delicata n. sp. (Heliodiscidae), Eucyrtidium granatum n. sp. (Eucyrtidiidae), Dictyoprora echidna n. sp., Spirocyrtis matsuokai n. sp. (Artostrobiidae), Elaphospyris cordiformis n. sp., Elaphospyris quadricornis n. sp. (Cephalospyrididae), Ceratocyrtis oconnori n. sp. (Lophophaenidae), Botryocella? alectrida n. sp., Pylobotrys? bineti n. sp. (Pylobotrydidae), Lychnocanium cheni n. sp., Lychnocanium cingulatum n. sp., Lychnocanium croizoni n. sp., Lychnocanium forficula n. sp. (Lithochytrididae), Apoplanius hyalinus n. sp., Apoplanius cryptodirus n. sp. (Lophocyrtiidae), Albatrossidium messiaeni n. sp., Phormocyrtis microtesta n. sp., Cryptocarpium? judoka n. sp. (Pterocorythidae), and Thyrsocyrtis kamikuri n. sp. (Theocotylidae). Biostratigraphic information is provided for each new species. In addition, we re-describe and illustrate the morphological variability of a remarkable Pterocyrtidium species formerly published by Bütschli (1882a).

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Applying a variational analysis, a minimum-enstrophy vortex in three-dimensional (3-D) fluids with continuous stratification is found, under the quasi-geostrophic hypothesis. The buoyancy frequency is held constant. This vortex is an ideal limiting state in a flow with an enstrophy decay while energy and generalized angular momentum remain fixed. The variational method used to obtain two-dimensional (2-D) minimum-enstrophy vortices is applied here to 3-D integral quantities. The solution from the first-order variation is expanded on a basis of orthogonal spherical Bessel functions. By computing second-order variations, the solution is found to be a true minimum in enstrophy. This solution is weakly unstable when inserted in a numerical code of the quasi-geostrophic equations. After a stage of linear instability, nonlinear wave interaction leads to the reorganization of this vortex into a tripolar vortex. Further work will relate our solution with maximal entropy 3-D vortices.

A mixed-layer kaolinite/smectite (K/S) containing trace amounts of quartz, discrete kaolinite, goethite-hematite, and calcite was hydrothermally reacted with deionized water at 150°, 200°, and 250°C for 1 to 12 months. The starting K/S contained 50% smectite consisting of 15% low-charge and 35% high-charge layers. The X-ray powder diffraction and chemical analyses of the reacted products indicated a progressive reaction from high-charge to low-charge smectite as a function of time and temperature. The reaction reached completion after 4 months at 250°C, at which point high-charge smectite layers entirely reacted to low-charge smectite layers, the latter maintaining a constant proportion of about 90% for longer run durations. For long reaction times, discrete kaolinite totally reacted, whereas quartz showed only partial dissolution and iron oxides remained stable. Thus, the reaction of high-charge to low-charge smectite layers may be expressed as: high-charge smectite + kaolinite (both interstratified and discrete component) + quartz → low-charge smectite.

The validity of the saddle/001 method for estimating the percentage of smectite layers in randomly interstratified illite/smectite (I/S) minerals as a routine laboratory technique has been examined with respect to the effects of the crystallite size distribution (N = number of layers) of I/S and the degree of preferred orientation of crystallites in the prepared specimen. X-ray powder diffraction experiments of I/S clays indicated that the crystallite size distribution was 3 < N < 12; these values were supported satisfactorily by the variation of the d(002) value of the samples. An analysis of the Lorentz factor concerning the degree of preferred orientation of crystallites indicated that a calibration curve calculated using the random powder Lorentz factor and the above crystallite size distribution fit the data better than an assumption of perfect orientation. Consequently, if a calibration curve of the saddle/001 ratio is used to estimate the percentage of smectite layers in I/S, an error of 10–15% should be expected from the variable crystallite size distribution of actual samples, in which I/S dominates over other phyllosilicate phases that give reflection between 10–14 Å. This method is useful, however, in estimating the relative percentage of smectite layers in randomly interstratified I/S for samples examined under identical experimental conditions.

Lithium-bearing donbassite and tosudite were found in veins in hydrothermally altered granite (Beauvoir granite) in the northern part of the Massif Central, France. The two minerals are characterized by their high Li contents and low Mg and Fe contents; their structural formulae are: $${\left( {S{i_{3.81}}A{l_{0.19}}} \right)_{\Sigma = 4.00}}{O_{10}}{\left( {A{l_{3.81}}L{i_{0.52}}Fe_{0.01}^{2 + }C{a_{0.02}}M{g_{0.01}}} \right)_{\Sigma - 4.38}}{\left( {OH} \right)_8}{\left( {N{a_{0.07}}{K_{0.04}}} \right)_{\Sigma = 0.11}}$$ for donbassite and $${\left( {S{i_{3.50}}A{l_{0.50}}} \right)_{\Sigma = 4.00}}{O_{10}}{\left( {A{l_{2.95}}L{i_{0.22}}Fe_{0.01}^{3 + }T{i_{0.01}}} \right)_{\Sigma = 3.19}}{\left( {OH} \right)_5}{\left( {C{a_{0.01}}N{a_{0.15}}{K_{0.18}}} \right)_{\Sigma = 0.34}}$$ for tosudite.

These chemical compositions indicate that the donbassite is an intermediate member of the donbassite-cookeite solid solution series and that the tosudite consists of interstratified Li-donbassite and beidellite. Both Li-bearing minerals show thermal behavior distinct from those previously reported for dioctahedral chlorite and tosudite.

Petrographie investigation of drill cuttings from the Echassières area indicates that the two minerals were formed in an intermediate stage of hydrothermal alteration following an early stage characterized by formation of muscovite (2M1) at >350°C and before the latest stage characterized by deposition of kaolinite and randomly interstratified illite/smectite at < 100°C. Moreover, tosudite occurs in the upper part of the granite, whereas donbassite is restricted to the lower part, suggesting the formation of tosudite at lower temperatures.

The chemical compositions of chlorite-smectite mixed-layered minerals (C/S) from the Ohyu caldera (Inoue, 1985) are analyzed using M+-4Si-3R2+ diagrams. The assumed original saponite has the following composition: Si3.54Al0.46O10Al0.173Fe2+1.385Mg1.295Mn0.02(OH)2M+0.56. Random C/S minerals (100 to 80% expandable layers) are interpreted as an interstratification of the starting 2:1 smectite layer with a A1XR2+3−x interlayer. The 2:1 smectite layer charge remains constant but Ca, Na, K cations are replaced by a Al-R2+ complex ion. The brucitic layer (produced by the polymerization of the complex ions) and the 2:1 smectite layer form a 14 Å non-expandable phase having a composition different from a true chlorite.

The true chlorite layers first appear in the ordered (corrensite) phase composed of a high charge saponite: Si3.35A10.65O10R2+3(OH)2M+0.65 and an octahedral vacancy-free chlorite Si2.90A11.10O10Al1.10R2+4.90(OH)8. The recrystallization of the original trioctahedral smectite into a high-charge saponite decreases the b-dimension difference with the chlorite component.

From these data, it is suggested that the trioctahedral smectite-to-chlorite conversion is controlled by three reactions: 1. fixation and polymerization of Al-R2+ complex ions in the interlayer region of the original smectite producing a 14 Å non-expandable phase (the interlayering of this phase with the original smectite gives the randomly interstratified C/S mineral. 2. dissolution of these random mixed-layered minerals and precipitation of corrensite. 3. dissolution of corrensite and growth of Fe-rich chlorite.

A mineralogical investigation of the highly kaolinized Chanon granite and albite-muscovite granite of the Montebras cupola, Creuse, France, indicates that the magmatic stage was followed by two hydrothermal events related to successive cooling stages and by late weathering. The hydrothermal alteration was accompanied first by greisen formation and then a broad kaolinization process, which pervasively affected the granitic bodies. In the Chanon granite, the greisens are characterized by a trilithionite-lepidolite-quartz-tourmaline assemblage and are surrounded by concentric alteration zones. From the greisen to the fresh granite three zones were distinguished: (1) a zone characterized by secondary brown biotite (<400°C), (2) a zone characterized by secondary green biotite and phengite (300–350°C), and (3) a zone characterized by the presence of corrensite (180°–200°C) located around greisen veinlets. In the albite-muscovite granite the greisen is composed of lepidolite and quartz. This mineral assemblage was followed locally by Li-tosudite crystallization. During the second hydrothermal event (<100°C) an assemblage of kaolinite, mixed-layer illite/smectite (I/S), and illite formed pervasively and in crack fillings; the smectite layers of the US are potassic. Weathering produced Fe oxide and kaolinite. This kind of alteration developed mainly in the overlying Chanon granite. Here, Ca-Mg-montmorillonite formed in subvertical cracks, which transect the two granitic bodies, and hydrothermal I/S was obliterated by Ca-Mg-montmorillonite.

The hydrothermal parageneses were apparently controlled by magmatic albitization and the bulk chemistry of the two granitic bodies. The albitization, the formation of large micaceous greisens, and the successive recrystallizations of biotite (which was the most susceptible phase to alteration) provide information on the temperature range and chemical mobility during successive cooling stages. Si and Mg activities increased as the temperature of alteration decreased, and secondary Mg-biotite and Mg-phengite crystallized as long as the K activity was sufficient. The crystallizations of secondary biotite and phengite were followed by the crystallization of I/S during stages of low K activity. Secondary hydrothermal phases in the Chanon granite contain substantial Fe and Mg. Secondary hydrothermal phases in the albite-muscovite granite contain only small amounts of Fe and Mg, suggesting a lack of chemical exchange between the enclosing Chanon granite and the albite-muscovite granite, which is depleted in Fe-Mg-rich primary phases, such as biotite.

X-ray diffraction and chemical analyses were performed on clay fractions separated from an acid brown soil (Dystrochrept) by means of size fractionations using high-gradient magnetic separation techniques. Breakdown of large phyllosilicates preexisting in the saprolite involved physical fragmentation and mineralogical transformations strongly related to chemical weathering.

Compared to the C horizon, the proportion of chlorite and vermiculite decreased strongly in the silt and coarse-clay fractions of the Al horizon, but was maintained in the finer clay fraction (< 1 μm). The distribution of mica in the different fractions was quite the opposite. Micas are the major component of the Al, 1–2 μm fractions, and their proportion progressively decreased with decreasing fraction size. Thus, it is concluded that during fragmentation and/or simple transformation of the larger phyllosilicates, clusters of chlorite, mica/vermiculite, and vermiculite layers were preferentially affected. A concentration of mica layers took place in the coarse clay fractions as chlorite and vermiculite residues were accumulated in the fine clays.

The process involved the loss of Fe and Mg, leaving, or forming, more aluminous dioctahedral minerals. As the transformation processes occurred, dissolution of preexisting minerals led to the precipitation of amorphous and/or crystalline Fe- and Al-oxides, and possibly of phyllosilicates. The new phyllosilicates appear to be montmorillonitic.

The most abundant end products of the weathering processes in either the Al or the Bw horizons appeared to be quite different. In the Al horizon they were identified mainly a hydroxyl-Al (Fe) intergrade smectite (montmorillonite), whereas in the Bw horizon the major component was an intergrade vermiculite originating, at least in part, from chlorite.

Nordstrandite from Lages represents the first occurrence of this mineral in an oxisoil that does not involve the influence of a calcareous substrate. This is also the first reported occurrence in Brazil. Nordstrandite occurs near the city of Lages only in the weathered bedrock facies, mostly where the circulation of meteoric water is restricted. There is also a close association between nordstrandite and the weathering of modified pseudoleucite structures. The interaction of meteoric water and feldspathic alkaline country rock with uncommon texture and mineralogy (rich in nepheline, sodalite, nosean, analcime and natrolite) promotes the development of solutions enriched in alkaline ions with basic pH, necessary to form nordstrandite. A detailed study by X-ray diffraction (XRD) and infrared (IR) spectroscopy in natural or chemically leached samples was performed to identify the Al(OH)3 polymorphs of gibbsite and nordstrandite.

The composition and origin of vanadium-bearing clay minerals in the Jurassic (Morrison and Entrada Formations) sandstones of the Colorado Plateau are reassessed using microanalyses (microprobe and scanning electron microscope). The main V-clays are authigenic illite and chlorite of various petrologic habits: clay casts and matrix, pore lining, replacement of detrital grains. The chemical composition of the V-clays is similar in three different localities in the Morrison Formation separated by about 50 km, suggesting that the V-clays are the result of a large regional event. In both illite and chlorite, Al and V are inversely correlated, showing that V replaces Al in the octahedral position. The chlorite contains a complex mixture of divalent and trivalent cations that cannot fit within a sudoite structure. A classification of V-micas is proposed that employs V3+/sum of the octahedral cations vs. the sum of the interlayer charges. V-illite and roscoelite from the Colorado Plateau are characteristic of diagenetic/hydrothermal environments. For a given locality the composition of the V-clays does not vary with habit, showing that these minerals formed at thermodynamic equilibrium.

The illitic end of mixed-layer illite-smectite series (I/S) in shales from Lower Cretaceous Barra de Itiúba Formation, Sergipe-Alagoas basin, was examined with X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). A mathematical decomposition of XRD patterns shows different I/S and illite populations. All the samples contain ordered (R = 1) I/S, poorly crystallized illite (PCI) and well crystallized illite (WCI). A randomly interstratified (R = 0) I/S was also identified in a fractured zone at 1020 m. The percentage of expandable layers in ordered I/S decrease progressively from 20% to 10%. TEM observations show a continuous change in morphology between two basic particle shapes: elongated (lath) and isometric. The size and morphology of particles change with increasing depth. The proportion of laths decreases while isometric particles become predominant. However, both particle types continuously grow and enrich the larger size fraction. The growth process is driven by a mass transfer from the dissolving small particles of predominantly I/S (R = 1) composition to the larger (more illitic) lath and isometric ones. The proportion of lath-shaped particles decreases with depth indicating that the more stable population upon increased burial is the isometric well crystallized illite (WCI) particles. Very large laths are observed in the fault zone where conditions may favor faster growth processes.

The smectite-to-illite diagenetic transformation has been documented in 5 different sedimentary basins using X-ray diffraction (XRD). Intermediate reaction products coexisting because of the effect of kinetics on this reaction have been characterized using decomposition of XRD patterns and comparison with calculated patterns. The nature and relative abundances of the various subpopulations of particles are shown to vary as a function of the geothermal gradient and of the age of the sediment. In all sedimentary basins that experienced a low steady geothermal gradient the physico-chemical characteristics (coherent scattering domain size [CSDS], junction probabilities) of intermediate mixed-layered illite-smectites (I-S) are similar. However, both the relative abundance and the crystallinity of the end-member illite increase as a function of the age of the sediment.

In basins that have experienced a higher geothermal gradient, the CSDS of the I-S subpopulation is higher for a given illite content, indicating a slightly different reaction pathway. This difference in the characteristics (peak position and width) of elementary peaks may be used to infer the presence of such a high geothermal gradient when no other data are conclusive. In this case the growth of the illite end-member is favored over the growth of intermediate I-S phases even in young basins. Illitic phases formed from the alteration of kaolin minerals exhibit characteristics similar to the reaction products of the smectite-to-illite diagenetic transformation in the case of a high geothermal gradient. In contrast with what is observed in shale diagenesis, the characteristics of the illitic subpopulations describe a continuum with absolutely no gap in between subpopulations. In sandstone reservoirs, the various subpopulations crystallize simultaneously from a kaolin precursor. As a consequence, no kinship is expected between the various subpopulations.

Shales and claystones in the Permian Irati Formation consist of Al-rich or Fe-Mg clay minerals in its southern/central and northern parts, respectively. The constrasting compositions indicate particular geological and paleo-environmental conditions. The purpose of this study was to determine the conditions of formation by characterizing the black shales and claystones from different sections of the northern edge of the basin, some of which reveal the presence of intruded diabase sills.

Black shales consist of saponite or saponite-talc mixed layers, talc, lizardite, nontronite, and quartz. Green claystones are nontronite-rich but also contain lizardite, talc, and quartz. The chemical compositions of the black shale and claystones, except for one sample (POR-56), exhibit a positive correlation of the TiO2, Cr, and P2O5 contents with Al2O3, which typically results from weathering processes. The presence of saponite, nontronite, and some accessory minerals (spinel, pyroxene, native silver) suggests altered basic-ultrabasic rocks as sediment sources, consistent with the rare earth element (REE) composition being less than the Post-Archean Average Shale (PAAS) or North American Shale Composite (NASC) levels and with negative Ce and Eu anomalies. Sample POR-56 consists largely of nontronite and is anomalously rich in zircon, monazite, and apatite. Chemically, sample POR-56 is different from the black shales and claystones, being richer in Al2O3-Fe2O3, MgO-poor, and having greater REE contents than the PAAS or NASC standards. The POR-56 bed is probably a bentonite resulting from the alteration of volcanic ash in sea water (strong, negative Ce anomaly). The Zr/TiO2vs. Nb/Y relation indicates that the magmatism was andesitic. During the Upper Permian, intermediate to basic volcanic activity was recorded in the Mitu Group of the Central Andes.

Close to the diabase sill, the black shales and claystones contain saponite, talc, and lizardite but nontronite is absent. Saponite and talc crystals, however, exhibit a larger coherent scattering domain size (CSDS) and are randomly oriented with respect to the sedimentary bedding. The thermal metamorphism effect is confirmed by the presence of secondary enstatite-augite and albite crystals.

Crystallization processes of the illite-smectite (I-S) mixed-layer mineral series during alteration of felsic vitric materials in volcaniclastic sediments through two drill holes (IT-2 and IT-8) near the Kakkonda active geothermal system, Japan, were examined by optical microscopy, scanning and transmission electron microscopy (SEM and TEM), electron microprobe analysis, X-ray diffraction (XRD), and oxygen isotope analysis. Temperatures measured through the drill holes increased nearly linearly with depth up to 317°C at the bottom (1700 m) of IT-8. Homogenization temperature measurements of fluid inclusions indicated that the alteration occurred at temperatures similar to the present temperatures. In selected volcaniclastic rocks, excluding andesitic rocks and black shales, clay minerals occurred as glass replacements and pore fillings as seen under SEM and optical microscopy, and exhibited predominantly euhedral hexagonal and elongated forms under TEM, implying that they precipitated in situ through hydrolytic reactions of glass and fluid. Based on XRD examination, I-S minerals showed a sigmoidal variation in illite layer percentage (%I) in the range of ∼150 to 220°C and R0 I-S minerals with intermediate %I between 20 and 40% rarely occurred (where R is the Reichweite parameter). The chemical composition also showed a specific variation with depth. Intermediate clays including smectite and I-S minerals are enriched in Al compared to those reported previously from hydrothermal alteration of almost equivalent parent rocks. The oxygen isotope data indicated that the reacting solution was percolating groundwater in the shallow levels and with fossil seawater in the deeper levels. Furthermore, calculating the fluid/rock (W/R) ratio from the isotope variations revealed that the alteration occurred at a nearly constant W/R ratio condition irrespective of %I. Consequently, the observed specific variations in structure and chemical composition of I-S minerals reflect the compositional variations of fluid participating in the crystallization at given temperatures under the conditions of a given original rock and constant W/R ratio. High pH and Na-rich solutions generated by progressive hydrolytic reactions between felsic glass and groundwater favored the precipitation of Al-rich smectite up to ∼150°C and was followed by precipitation of an aluminous R1 I-S mineral with few intermediate R0 I-S minerals at higher temperatures. The crystallization obeys Ostwald’s step rule behavior of smectite illitization processes under a high geothermal gradient.

A clay-rich Callovo-Oxfordian sedimentary formation was selected in the eastern Paris Basin (MHM site) to host an underground laboratory dedicated to the assessment of nuclear waste-disposal feasibility in deep geological formations. As described initially, this formation shows a mineralogical transition from an illite-smectite (I–S) mixed-layered mineral (MLM), which is essentially smectitic and randomly interstratified (R = 0) in the top part of the series to a more illitic, ordered (R ⩾ 1) I–S in its deeper part.

This description has been challenged by using the multi-specimen method developed by Drits et al. (1997a) and Sakharov et al. (1999). It is shown that all samples contain a physical mixture of an unusually (?) illitic (∼65% I) randomly interstratified I-Exp (illite-expandable MLM) and of a discrete smectite, in addition to discrete illite, kaolinite and chlorite. Structural parameters of the different clay phases vary little throughout the series. According to the proposed model, the mineralogical transition corresponds to the disappearance of smectite with increasing burial depth.

Comparison with clay minerals from formations of similar age (Oxfordian-Toarcian) throughout the Paris Basin shows that the clay mineralogy in the deeper part of the series originates from a smectite-to-illite transition resulting from a low-temperature burial diagenesis. The anomalous lack of evolution of clay minerals in the upper part of the series is thought to be related to specific interactions between organic matter and clay minerals.

Clay minerals in chilled or brecciated margins (altered glass) and massive inner crystalline parts (mesostasis) of three basalt-hawaiite bodies from Mururoa Atoll (French Polynesia) have been studied in order to compare their chemical and mineralogical compositions. Polyphase assemblages comprise di- and trioctahedral phases, both of which consist of non-expandable layers (chlorite, celadonite) and two types of expandable layers (saponite and Fe-rich smectite or ‘nontronite-like’ material). The presence of the Fe-rich clays is supported by the presence of the X-ray diffraction 060 peak at 1.51–1.52 Å and of the infrared absorption bands at 875 and 822 cm−1 (Fe3+-Al-OH and Fe3+-Fe3+-OH groups, respectively). The chemical composition of the Fe-rich smectites does not fit with the theoretical nontronite field. The layer charge averages 1 per Si4O10 making these Fe-rich smectites close to ‘celadonite-type’ clays. This could explain the presence of mixed-layer celadonite-smectite. Plotted in an M+/4Si vs. Fe/sum octahedral cations diagram, the chemical compositions of clay minerals in the mesostasis form a continuous field limited by the celadonite-high-charge nontronite-like smectite and chlorite end-members. The clay assemblages are different from those formed in hydrothermal systems or low-grade metamorphic conditions which are characterized by the sequence: saponite → randomly ordered chlorite-smectite mixed-layered minerals (MLMs) → corrensite → chlorite. The systematic presence of Fe-rich clays either in the altered chilled margins or in the massive inner parts of the basalt-hawaiite bodies (high-charge nontronite-like smectite and mixed-layer nontronite-celadonite) makes the Mururoa sea-mount a potential terrestrial analogue for Mars surface exploration.

The Gourougou volcanic massif (northeastern Morocco) is actively prospected for bentonite deposits. Five bentonites originating from different environments were selected for the present study: hydrothermal alteration of obsidian perlite glass inside the volcanoes themselves (Providencia and Tribia deposits); alteration of pyroclastic flows in a marine shallow water to lagoonal lacustrine environment (Ibourhardayn deposit); ash falls in marine or lacustrine systems (Moulay Rachid and Melg el Ouidan (formerly Camp Berteau) deposits). All of these bentonites were probably formed from volcanic glass originating from a rhyolitic magma at different stages of differentiation as shown by slight variations of REE and incompatible element abundances. The crystal-chemical characteristics of the smectite vary according to alteration conditions: beidellite predominates in hydrothermal systems, whereas montmorillonite predominates in lagoonal and lacustrine environments, and mixed-layer beidellite-montmorillonite in the sea-water-altered pyroclastic flows. All these dioctahedral smectites exhibit a heterogeneous distribution of charge as shown by the presence of partially expandable (1 EG) or non- expandable (0 EG) layers in the K-saturation state. The proportion of the collapsed or partially expandable layers is not related to the average layer charge or to the cation exchange capacity. This militates for an overall heterogeneous charge distribution. Compared to other natural or experimental alteration systems of similar rhyolitic glass, the formation of beidellite or montmorillonite appears to be controlled by the amounts of Mg in the system.