Isotherms were obtained for nitrogen adsorption and desorption on seven halloysite-rich samples from New Zealand and Western Australia. Calculations from these isotherms indicate that halloysites with mainly small particles (< c. 0.08 μm in width) had abundant cylindrical pores with narrow size distributions in the 5-15 nm range. They also indicate that halloysites with mainly large particles (> c. 0.1 μm in width) had few if any pores in the mesopore range (2–50 nm). Transmission electron microscopy (TEM) shows that cylindrical pores originate from the central holes in tubular particles. The TEM also suggests that slit-shaped pores can originate from the shrinkage of blocks of layers upon dehydration of halloysite.

The rheology of aqueous suspensions of Na halloysites with different particle shape has been investigated using a Haake rotary viscometer. Three halloysites from New Zealand were used: Matauri Bay (MB), Te Akatea (TA) and Opotiki (Op) which are mainly composed of thick long tubules, short thin laths, and spherules, respectively. Suspensions of the materials subsequently prepared from the MB and TA samples show a pseudoplastic consistency under shear, characterized by a steep initial rise in shear stress as shear rate increases, followed by a linear increase in stress when a certain shear rate is exceeded. The Op halloysite, on the other hand, shows Newtonian flow behaviour for which shear stress increases linearly with shear rate throughout. For MB and TA, the shear stress developed during rotor acceleration is larger than that produced during deceleration, and the corresponding flow curves enclose a hysteresis loop. As suspension pH increases, the pseudoplastic character decreases as does the amount of hysteresis. Above pH 7.5, flow approaches Newtonian and hysteresis is absent. Plots of Bingham yield value against pH at different ionic strengths (0.003, 0.03 and 0.3 M NaCl) intersect at pH 6.0 for MB and at pH 7.1 for TA. These values are identified with the point of zero charge (PZC) of the particle edge surface. The flow characteristics of halloysites may be explained in terms of the influence of particle shape, pH, electrolyte concentrations, and layer composition on particle interactions.

The comparison between measured and predicted smectite percent (%Sm) in an illite-smectite (I-S) mixed-layer series was used to estimate the thermal conditions of diagenesis in the Ardèche sedimentary series. Measurements were performed using the decomposition procedure (Lanson & Besson, 1992) of XRD patterns obtained from oriented preparations (<0.2 μm fractions). Three particle populations were identified: I-S, poorly crystallized illite (PCI), and well crystallized illite (WCI); the %Sm was measured in the I-S population by comparison with calculated XRD patterns using the NEWMOD software (Reynolds, 1985). The theoretical evolution of %Sm with depth obtained with the two first-order kinetic reaction processes described by Velde & Vasseur (1992) was compared to the measured one at Balazuc. The best fit was obtained for the following conditions: 35°C km–1 and between 1500 and 2000 m for the thermal gradient and the eroded piles, respectively. The predicted values for I-S compositions in the 10–0% Sm range are overestimated by the model because the reaction controlling the composition is no longer the dissolution of I-S but the ripening of illitic particles (PCI and WCI).

Two zones can be distinguished in the sedimentary series: (1) down to 55 m, the %Sm of I-S particles is highly variable and seems to be controlled by local variations in permeability and chemical composition; (2) down to 550 m, the %Sm of I-S particles is more strictly dependent on the general time-temperature conditions. An anomalously high %Sm value is located in the vicinity of faults at 1669 m due to local change of the water/rock ratio.

The clay mineral distribution in the Early Cretaceous depositional sequences along the Cameros Basin has been established on the basis of XRD traces and TEM/EDAX analyses. Samples from the Latest Berriasian-Barremian depositional sequences are characteristic of epimetamorphic conditions. Illite ‘crystallinities’ are broader than expected (0.35–0.490°Δ2θ), due to the consistent presence of K-mica-paragonite mixed-layer and discrete paragonite associated with the illite 10 Å peak. The Late Barremian-Early Aptian depositional sequence, around the depocentral sector of the basin, represents a sudden change to anchimetamorphic conditions, marked by the presence of pyrophyllite and rectorite and by a significant decrease in the A1IV content of the chlorites. Towards the northwestern border of the basin, this sequence was affected by deep diagenetic conditions, as deduced from the clay mineral association and the ‘crystallinity’ values (0.57°Δ2θ). The changes in the clay mineral assemblages and ‘crystallinity’ data can hardly be explained in terms of the varying burial depth and are related to changes in the circulation of fluids associated with varying facies (modal composition, grain size). Permeability is regarded as the main factor controlling the circulation of these migratory fluids.

: Smectite genesis in two granitic saprolites was studied, using qualitative and quantitative mineralogical methods and high resolution transmission electron microscopy (HRTEM). The primary minerals (plagioclase and mica) give rise to the formation of different kinds of smectites according to the weathering conditions (pH and drainage). Under a relatively basic, drained environment, a neoformed montmorillonite with a spheroidal organization exists in fillings of plagioclase cores. In the same conditions biotites are transformed into beidellites with a quasi-crystal organization. Under hydromorphic conditions, muscovites evolve incompletely towards smectites, whereas biotites lead to a montmorillonite with a tactoid organization.

Mineralogical and water adsorption properties of water dispersible clays extracted from five soils of different typology after treatment with acid to different pH levels, were studied. The mineral composition, total and divalent iron content, surface areas and average adsorption energies of water dispersible clays were complicated functions of pH, reflecting the simultaneous effects of mineral destruction and aggregate disruption processes under influence of protons on soils. The magnetic susceptibilities of water dispersible clays were the lowest at pH 2 and roughly constant at higher pH values indicating the dissolution of crystalline forms of Fe below pH 3. The broadening of the peaks of adsorption energy distribution functions with decrease in pH is related to increasing formation of amorphous material from mineral phases.

Distribution of Fe in the fine fractions of four Czech bentonites was investigated by M6ssbauer spectroscopy. The spectra at room and liquid nitrogen temperatures revealed that most Fe present in the samples is structurally bound in smectite. Microcrystalline and/or Al-substituted goethite was identified in all fine fractions, comprising 8 to 50% of total Fe. This mineral was partly magnetically ordered in the Rokle sample even at room temperature. Two per cent of total Fe was bound in hematite in the Krásný Dvoreček sample. Only octahedral Fe(III) was found in the Rokle and Stebno samples, while Krásný Dvoreček and Hroznětín contained 9 and 38%, respectively, of the total Fe as octahedral Fe(II) and 14% of total Fe was found as tetrahedral Fe(III) in Krásný Dvoreček.

Authigenic chrysotile, stevensite, calcite, aragonite and pectolite have formed together in a Holocene ophiolitic debris flow in Southland, New Zealand. Mineral growth occurred about 4700-5700 years ago. The temperature of formation of these minerals is estimated from climatological data to be 5–10°C Surface water and groundwater δ180 is currently about –10‰, and was estimated to be about –9.5±1‰ during mineralization. Coexisting calcite (δ180 = +23‰) and aragonite (δl8O = +24‰) were in equilibrium with each other and with the groundwater at 5–10°C Stevensite δ180 is +14 to +16‰, chrysotile has δ180 = +5.5‰, and authigenic pectolite has δ180 near +10‰. Carbon isotope ratios for calcite and aragonite are strongly depleted (δ13C = –13 to –18) which suggests that dissolved CO2 had δ13C below -27. This isotopically light carbon probably resulted from a high organic component of carbon dissolved in the groundwater.