In electric fields, anisodiametric mineral particles in suspension orientate and align. When tagged with fluorescent molecules, the alignment is accompanied by changes in the intensities of the polarized components of the emitted fluorescence. By measuring these changes under specific experimental conditions, any non-random directional coincidence of the absorption and emission transition moments associated with the dye molecules can be evaluated and the spatial array of the dyes estimated. From such measurements, the binding of the optical brightening agent FBA1, a triazinylaminostilbene compound, to sepiolite has been studied.

The chemical composition of about 500 diagenetic chlorites, determined by electron microprobe, has been studied in six different sedimentary sequences spanning conditions from early diagenesis to low-grade metamorphism, in the temperature range 40–330°C. The range of Fe/(Fe + Mg) is almost complete and is positively correlated with Al. Five sequences show the same compositional variation. In each, the most siliceous chlorites have the lowest R2+, substantially more octahedral than tetrahedral Al, and the lowest octahedral totals. Conversely, the least siliceous have the highest R2+, nearly equal octahedral and tetrahedral Al, and octahedral totals close to that for an ideal trioctahedral mineral. A dioctahedral substitution Si[]R2−2 (where [] represents a vacant octahedral site) which decreases with temperature, describes this variation. Low octahedral totals are, however, induced by the method of calculation and need not indicate vacancies; for published wet chemical analyses of metamorphic chlorites they may simply indicate oxidation of Fe. Intergrown dioctahedral phyllosilicates may partly account for apparent vacancies in diagenetic chlorites. Nevertheless, the correlation of composition with temperature and similarities to the temperature-related evolution of synthetic chlorites, suggest that diagenetic chlorites are compositionally distinct from, but metastable with respect to, fully trioctahedral metamorphic chlorites. Temperature-related trends are modified by bulk composition, complicating their potential use for low-temperature geothermometry.

An intergradient 14 Å mineral showing X-ray diffraction features of “chloritized” vermiculite in a Korean Ultisol was studied. The structural formula of the whole 2:1 layer-silicate (14 Å mineral and mica) in the Na+-saturated 0·2–0·5 µm fraction was obtained by elemental, thermogravimetric and 29Si and 27Al nuclear magnetic resonance spectroscopic analyses in combination with extraction of the interlayer material from the 14 Å mineral by hot 1/3 m sodium citrate treatment. This formula showed: (1) the 2 : 1 layer contains nearly one Al3+ in four tetrahedral positions, and Al3+ is the dominant cation in the octahedral sheet; (2) K+, exchangeable Na+ and sodium citrate extractable 1 : 1 layer occupy the interlayer space of the 14 Å mineral in similar proportions. Very little interlayer K was replaced by Na+ during the citrate treatment. Possible schemes of alteration of the 2 : 1 layer to the 1 : 1 layer as its interlayer material are discussed.

Samples of the mineral pyroaurite, formed from the weathering of partially serpentinised harzburgite (olivine + pyroxene) were found in an arid region of the Sultanate of Oman. These were either golden or silver in colour depending on the horizon from which they were derived. Chemical analysis showed that the colour variation was primarily due to the differing conditions in the hydrological environment. The golden colour was attributed to small Fe(III) oxide particles detected by Mössbauer spectroscopy. In addition, the samples were examined by X-ray diffraction, scanning electron microscopy, and glycerol intercalation. These results were compared with a synthetic pyroaurite sample prepared under conditions (previously reported) similar to those in nature. These conditions are shown to approximate to those found in the hydrological environment in the zones of the natural pyroaurite formation.

Chemical variations in individual chlorite crystals of diagenetic origin delineated by energy dispersive X-ray spectroscopy (EDS) in a transmission electron microscope (TEM) indicate a temperature dependent chemical zonation in each grain. Silicon decreases and Al increases with higher temperature resulting in a decreasing Si/Al ratio away from the crystal core reflecting the time and rate of the crystal growth. Chlorite particle-size distributions obtained by scanning electron microscopy (SEM) give steady state profiles which suggests that the chlorite growth is controlled by a grain coarsening process related to Ostwald ripening.

The Kämpf & Schwertmann (1982) procedure for concentrating iron oxides in soil clays by dissolution of kaolin and gibbsite by boiling for 1 h in 5 m NaOH may not dissolve all kaolin, and also results in the precipitation of sodalite. For the complete dissolution of kaolin in kaolin-rich soil clays a boiling time of 2 h in 5 m NaOH was required. The large amounts of sodalite produced were not removed by the prescribed single wash in 0·5 m HCl. Oxalate soluble Al contents of iron oxide concentrates were sometimes very high and dithionite Fe contents were very low both in concentrates containing sodalite, and in those for which sodalite was not detected by XRD, but where a previously unsuspected amorphous sodalite-like phase may have been present. Complete removal of precipitated sodalite was achieved by two extractions with 0·5 m HCl at 25°C for 20 min. This modified procedure does not alter the Al-substitution and crystal size of goethite, hematite and maghemite as determined by XRD measurements.

Strongly held carbonates anions in the interlayer region of pyroaurite-type compounds, [MlII1−xM2IIIx(OH)2]x+[(CO3)x/2yH2O]x− (x = 0·15−0·44), can be relatively easily exchanged by other anions such as NO3−, Cl− or SO42− dissolved in heated glycerol. Some Fe(III) of pyroaurite is reduced to Fe(II) by the glycerol treatment. If pyroaurite is treated with glycerol in the absence of dissolved anions or with glycerol vapour at 120°C, glycerol becomes intercalated in the interlayers. In all examples the interlayer CO32− is partially or completely lost as CO2. In aqueous salt solutions a glycerol intercalated form allows other anions to substitute in the interlayer. Expansion in the c-axis direction following glycerol treatment depends on (1) the method of glycerol treatment, (2) the trivalent metal in the octahedral sheet, and (3) the interlayer anions. Heated glycerol causes a different expansion to that produced by its vapour phase at 120°C. The variation in d(003) follows the series: hydrotalcitevap. > pyroauritevap. > hydrotalciteliquid > pyroauriteliquid > SO42−-pyroauritevap. > SO42−-hydrotalcitevap., where liquid refers to glycerol used at 160–180°C and vap. refers to glycerol vapour at 120°C Carbonate-free, glycerol-intercalated pyroaurite compounds may serve as re-usable anion absorbers. Glycerol intercalates of pyroaurite-type compounds may also be useful to study and identify stacking sequences and interlayer compositions in these minerals.

Centrifugal photosedimentation was used to determine the size distribution of dilute bentonite suspensions as a function of saturating cation. This method is shown to give a better estimate of the effect of saturating cation on tactoid size than the techniques that are currently used. The results indicate that tactoids may occur in preferred size ranges.

Structural features of very highly disordered 2:1 trioctahedral phyllosilicates from the Madrid Basin have been studied. Application of Fourier methods to XRD patterns shows that these materials consist of random kerolite-stevensite mixed-layered phases (R = 0) with 50–80% kerolite layers, and have a very small particle size with a mean of three unit-cells stacked in the c* direction. IR spectrum deconvolution in OH-stretching and librational modes seems to indicate five different types of water. Specific surface measurements (N2, BET) indicate anomalous high values (240–320 m2/g). These results suggest important catalytic and surface chemistry applications.

Three bentonites, from Bavaria, Wyoming and Brazil, were separated into various fractions. The layer charge was determined by alkylammonium ion exchange and increases with particle size from 0·25 Eq/(Si, Al)4O10 (<0·06 µm) to 0·28 Eq/(Si, Al)4O10 (1–10 µm). The charge density corresponds to an interlayer cation density of 0·75–0·80 mEq/g silicate. Total amounts of 0·90–1·0 mEq of different surfactant cations (dimethyl dioctadecylammonium, trimethyl tetradecylammonium, alkylammonium ions) are bound per gram silicate. The difference between the total and the interlayer amount of surfactant ions decreases with increasing particle size. The amounts exceeding the interlayer CEC are bound at the edges. Tetramethylammonium (TM) ions restrict the interlayer adsorption of long-chain quaternary alkylammonium ions such as trimethyl tetradecylammonium (TMTD) ions, and only monolayers of flat-lying surfactants are formed. A ratio of TMTD and TM is attained which leads to densely packed monolayers of organic ions. The collapsing effect is smaller for tetraethylammonium ions so that considerable amounts of TMTD ions are adsorbed in bilayers. When bentonites are reacted with quaternary alkylammonium ions of technical quality some selectivity is observed according to particle size and layer charge. Smaller particles with lower charge density preferentially bind the longer chain compounds, whereas large particles with higher charge density select smaller sized surfactants.

The Tertiary sequences in northern Kyushu, Japan, contain several types of zeolite and clay minerals together with carbonaceous materials. A correlation between authigenic mineral zones and vitrinite reflectance reveals the delay in mineral authigenesis relative to the increase in vitrinite reflectance compared with similar studies in other regions. This may be ascribed to causes such as high paleogeothermal gradient, and chemical composition of pore-waters and host sediment.

Four 15 g samples of an unsedimented Wyoming bentonite were treated with 200 cm3 of 0·025, 0·050, 0·100 and 0·250 mol dm−3 H2SO4 for 1 h at room temperature (samples I–IV, respectively). Three further 15 g samples were treated with 200 cm3 of 50% (v/v) H2SO4 for 1 h at 20°C (sample V), and 1 and 2 h under reflux (samples VI and VII, respectively). X-ray fluorescence and diffraction studies revealed that only samples VI and VII suffered any substantial structural attack. The resulting acidity of the clays, determined by cyclohexylamine desorption, indicated that sample V contained the largest number of protons at 0·59 mmol H+ (g clay)−1. Sample V was also the most efficient catalyst for the dehydration and etherification of hexan-1-ol, giving a combined product yield of 17·0% after 2 h reflux in neat reactant. The parent bentonite and samples I and II showed no discernible catalytic activity despite measured acidities of 0·1, 0·24 and 0·34 mmol H+ (g clay)−1. In contrast samples III and IV gave combined product yields of 4·5 and 11·0%, respectively, which correlated well with the measured acidities of 0·38 and 0·48 mmol H+ (g clay)−1. Samples VI and VII, prepared by reflux in acid, contained 0·3 and 0·1 mmol H+ (g clay)−1, respectively, and gave combined product yields of 13·0 and 6·0%.

The acidity of Ni2+- and Co2+-exchanged montmorillonite has been probed using the diagnostic bases n-butylamine, cyclohexylamine and pyridine. Derivative thermograms for the desorption of pyridine from Ni2+- and Co2+-exchanged montmorillonite exhibited strong maxima at 40°, 90° and 360°C together with a weak maximum near 170°C The desorption maximum at 360°C is usually attributed to desorption of base from Bronsted acid sites. However, IR spectra of pyridine adsorbed on Ni2+- and Co2+-exchanged montmorillonite, at 250°C were dominated by intense bands near 1450 and 1607 cm−1 which are diagnostic of Lewis-bound pyridine. Consequently, the desorption maximum at 360°C must, in this instance, be attributed to desorption of pyridine from Lewis acid centres. Other bases, including cyclohexylamine and butylamine, also desorb at temperatures which have previously been attributed to the desorption of protonated base. Ni2+- and Co2+-exchanged clay contained predominatly Lewis acid or electron accepting sites, which is in marked contrast to the behaviour of trivalent cation exchanged clays.

The adsorption of acrylonitrile (AN) monomer vapour in the interlamellar space of smectites exchanged with different cations (Na or Y or hexylammonium) was monitored and used to yield macromolecular layers. Polymerization in the presence or absence of a free-radical initiator was obtained by heating at 100°C for 72 h. Cyclization can already be obtained at this stage, and is completed by heating the polyacrylonitrile (PAN)-complexes at 220°C for 48 h.

The sequential development of kaolin by progressive alteration of smectite, involving kaolin-smectite interstratifications as a genetic link is described from a red and black complex. Mineral compositions were studied using XRD, DTA and XRF techniques. The basalt-derived soils are situated along a 600 m transect and grade in colour from dark grey (10 YR 3/1) to red (5 YR 3/3). The kaolin proportions in the interstratification increase almost linearly with increasing reddening up to ∼80%. Whole-soil chemical analyses exhibit no significant variations in the major element composition, but dithionite extractable Fe increases along the transect from 1% to 4·16%. Hematite and goethite are the only secondary iron phases. Topographic differences are slight but sub-surface bedrock contours plus appreciable variations in sand content between red and black soils could be genetically significant.

Genetically homogeneous clay fractions are not always available for K-Ar isotopic dating of authigenic sedimentary material, particularly when dating illitic mixed-layer clay minerals. Three populations of mixed-layer clay minerals have been recognized in Upper Triassic sandstones from the Paris Basin (France), their occurrences being related to the flow of allochthonous fluids across the stratigraphic sections of the basin during Mesozoic times. A method is described for interpreting the K-Ar mixture ages obtained on carefully selected fractions, resulting in constraints being able to be made on the timing of the movements of these fluids.

Discrepancies between clay mineral and organic indicators of very low-grade metamorphism have been observed from the Southern Uplands of Scotland. In the Southern Belt, I-S expandability ranges from 18–5% and chitinozoan reflectance from 0·8–2·1% R0 mean; a clear correlation exists between I-S expandability and organic maturity. At Dob's Linn in the Central Belt, I-S expandabilities range from 18–10%, and chitinozoan reflectance from 3·6–4·8% R0 mean. The results from Dob's Linn show anomalously high I-S expandabilities with respect to maturity, both in comparison with the Southern Belt and with previous work from other regions. K-feldspar is present in variable amounts in the Southern Belt, but is not detectable by XRD at Dob's Linn. Low K+ activity is believed to have resulted in a slower reaction rate at Dob's Linn, and a consequent “lag” in I-S expandability with respect to the Southern Belt.

Smectites in the montmorillonite-beidellite pseudo-binary system were synthesized from glass at the hydrothermal conditions 100 MPa and 250–500°C. Products were analysed by X-ray powder diffraction for randomly oriented and glycolated samples, and also according to the Greene-Kelly test. A new mixed-layer mineral consisting of regularly interstratified montmorillonite-beidellite was found below 400°C for M50B50 composition, where M and B denote the compositions of ideal Na-montmorillonite and Na-beidellite, respectively. Montmorillonite was obtained as a single phase below 375°C in the composition range from M100B0 to M78B22. Above 375°C, montmorillonite decomposed into an assemblage of beidellite, saponite and a silica mineral. Beidellite as a single phase was synthesized below 400°C for M0B100 composition. Above 450°C, Na-rectorite (regularly interstratified paragonite-beidellite), Mg-free dioctahedral smectite and/or Mg-rich trioctahedral smectite appeared together with silica minerals. These smectites showed the same swelling behaviour as that of montmorillonite. Phase relations in the montmorillonite-beidellite pseudo-binary system indicate no complete solid-solution series.

La fixation du toluène et sa polymérisation dans les espaces interfoliaires d'une montmorillonite-Cu(II) au cours de cycles de déshydratation, adsorption, désorption de l'excès de réactif et réhydratation, ont été étudiées. Elles ont été suivies au moyen de diverses méthodes d'analyse (thermogravimétrie, radiocristallographie et spectrophotométrie d'absorption infrarouge). Les résultats rappellent ceux obtenus lors de l'étude du système montmorillonite-Cu(II)-benzène. Ainsi, la fixation du toluène s'effectue selon deux réactions, correspondant l'une à l'adsorption d'une molécule de toluène, l-autre à celle de trois molécules de toluène par ion Cu2+. Toutefois, l'affinité du toluène pour la montmorillonite est supérieure à celle du benzène.

The thermal behaviour of sepiolite and palygorskite treated with pyridine (Py) was investigated by DTA, TG, DTG and EGA (by MS) under a flow of air and inert gases (N2 or Ar). The thermal analysis showed that the organic base was adsorbed by the clays, penetrating into the clay pores and replacing zeolitic and bound water. Its presence in the pores shifted the dehydroxylation peak to temperatures higher than the corresponding peak in the untreated clays. Under N2 and Ar, thermal desorption of Py from sepiolite was observed at 260 and 650°C whereas for palygorskite only traces of Py were detected in the evolved gases. In addition to desorption, reactions of pyrolysis and condensation to coke were detected by the evolution of ammonia, methane and hydrogen, respectively. In air, oxidation of the organic matter led to the appearance of exothermic peaks. The profile of the DTA curve and the temperatures of the most intense exothermic peaks were determined by the rate of the carbon oxidation.