The aim of this research was to determine the temperature of kaolin calcination in order to obtain an intermediate product (metakaolin) for the synthesis of geopolymers with potential application as self-supporting zeolitic membranes. The products obtained were analysed with X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The structural analysis of the metakaolins obtained suggested that the optimal temperature for the proposed application is 700°C. After alkali activation of metakaolin, it is possible to obtain zeolite A and hydroxysodalite. The factors analysed, determining the type and quantity of crystalline phases, were activation temperature and concentration of sodium hydroxide solution (activator). The largest amounts of zeolites were obtained by alkali activation with 9 mol/dm3 NaOH solution at 70°C.

The planned final disposal repositories of spent nuclear fuel in several countries, including Finland, pose significant scientific challenges due to their extremely long lifespan. One of the key materials proposed for use in Posiva Oy's repository in Finland is MX-80 bentonite in a compacted, water-saturated state. Border cases of calcium and sodium forms of purified bentonite were included in this study. The MX-80 in the repository is expected to undergo cation exchange due to the composition of the groundwater. The clays were studied at different dry densities between 0.7 and 1.6 g cm–3. The microstructure of the water-saturated, compacted clays was investigated using small-angle X-ray scattering, nuclear magnetic resonance and transmission electron microscopy. Additionally, atomic force microscopy was used to characterize the shape and size of the fine-fraction clay platelets. As expected, the average shape of the fine fractions was smaller than the bulk material, but a more elongated shape was present in the purified material. Mainly due to sample density, the pore structure was noticeably different for the Na form of purified bentonite at 0.7 g cm–3 density, but at higher degrees of compaction, no significant differences were noted between the samples. The laboratory results obtained in this study could be useful for safety and performance analysis of this high-level waste repository where sodium bentonite is used and is expected to change its charge-compensating cation composition during the repository's lifetime. Microstructural data may be used in modelling of diffusion and sorption by surface complexation modelling, for example, or as a basis for mechanical and water transport models.

Nitrogen adsorption isotherms were measured on synthetic 2-line and 6-line ferrihydrites heated to 400 K, 500 K, and 600 K under dry conditions for different times ranging from 4 to 3000 h. Evaluation of specific surface area, microporosity and fractal dimension revealed that 2-line and 6-line ferrihydrites are highly microporous powders consisting of aggregates with corrugated interior and exterior surfaces. Furthermore, the surfaces of the single particles forming the aggregates have a smaller fractal dimension, i.e. a smoother appearance, than those of the entire aggregate. The diffusion of water lost during the heating process is influenced by the size of the micropores. The initial stage of the dehydration of the ferrihydrites can be described as similar to the process of Ostwald ripening.

Three raw samples of Fe-rich smectites from Gafsa (Jebels Shemsi and Hammadi, Tunisia) have been characterized by different techniques which indicate that they contain (15 – 20%) illite, probably interstratified and to a lesser extent they also contain kaolinite, calcite, quartz and Fe oxides. These samples present a relatively high Fe content (∼9%) in the <2 μm fraction. From EPR and Mössbauer spectroscopy it is deduced that Fe is mainly present as Fe(III) in the octahedral environment of smectites and also in Fe-oxyhydroxides associated with the clays. Aluminium-pillared clays have been prepared from the Na+-purified samples, and their thermal stability and acidity have been studied.

The dehydration of hexadecyltrimethylammonium (HDTMA)-exchanged smectites has been studied using X-ray diffractometry (XRD) and differential scanning calorimetry (DSC). The basal spacing of hydrated HDTMA-smectites changed with temperature. The 2.5 HDTMA-smectite (i.e. smectite treated with HDTMA equivalent to 2.5 times the CEC) showed a continuous increase in its basal spacing during dehydration up to 200ºC, while the 1.2 HDTMA-smectite showed a significant decrease in basal spacing. It is assumed that the less ordered alkyl chains in the wet state in the interlayer region may be rearranged to ordered chains (e.g. all-trans conformation) during sequential dehydration. This results in a decrease in interlayer spacing in the phase with low organic packing density and a flat-lying array (i.e. 1.2 HDTMA-smectite), and a gradual increase in the basal spacing when the chains have a vertical configuration (2.5 HDTMA-smectite).

Clay minerals of several hydrothermally altered zones in a 1200-m biotite-granite core from a drillhole in northern Switzerland were studied microscopically, by XRD and by electron microprobe. The minerals principally affected by the hydrothermal alteration were plagioclase (An5-An20) and, to a lesser extent, biotite. Illite, regularly interstratified illite-smectite and dioctahedral chlorite-smectite, dioctahedral chlorite, trioctahedral chlorite and kaolinite were detected in the alteration products. Commonly, two or more clay minerals occurred together in pseudomorphs after plagioclase. The mineral chemistry of the clay minerals showed a predominance of the substitution KAl for Si and, to a lesser extent, MgSi for Al. Fluid-inclusion data and the absence of pure smectite and epidote indicated temperatures of ∼200°C for the fluid that caused this alteration.

Comparison of the adsorptive properties of two samples of akaganéite prepared by different methods shows that a structural scheme based upon solid rods is much more likely than a previously proposed scheme involving tubes. Specific surface areas, qualitative and quantitative assessments of porosity' and electron micrographs strongly support this structure.

The composition, morphology and crystal order of clay minerals in silt-sized sediments carried in suspensions from 25 major rivers across tropical southern Africa have been studied by X-ray diffractometry and scanning and transmission electron microscopy. Our goal was to determine the spatial variability of clay-mineral associations in diverse geological settings, and in climatic conditions ranging from humid Angola and Zambia to hyperarid Namibia and the Kalahari. Specific attention was paid to the micromorphology and chemical composition of smectite particles. The relative abundance of smectites, illite/mica, kaolinite and chlorite enabled identification of regions characterized by different physical and chemical processes: (1) negligible chemical weathering is documented in Namibia, where river muds mostly contain illite/mica or smectite derived from Damara metasedimentary or Etendeka volcanic rocks; (2) kaolinite documenting intense weathering, reaches a maximum in the Okavango, Kwando and Upper Zambezi, sourced in subequatorial Angola and Zambia; (3) suspended-load muds in the Limpopo and middle Zambezi catchments display intermediate features, with varied assemblages and smectite compositions reflecting diverse parent lithologies. Clay mineralogy and chemical composition are confirmed as a most effective tool to unravel present and past climatic conditions on a continental scale.

The composition and particle morphology of diagenetic mixed-layer illite-smectite (I-S) in the shallow buried Ordovician Kinnekulle K-bentonite were studied to understand the process of illitization in the Baltic Basin. The same K-bentonite bed from 12 different locations in the Basin was sampled and analysed by means of X-ray diffraction (XRD), atomic-force microscopy (AFM) and K-Ar dating. Illite-smectite in the samples was identified as a highly illitic R1 type illite-smectite vermiculite (high-charge smectite) mixed-layer mineral with 63–78% illitic layers. Illite-smectite was characterized by log-normally distributed thin particles with an area-weighted mean thickness varying from 1.9 to 3.6 nm and 2.1 to 3.8 nm by XRD-PVP and AFM analysis, respectively. The K-Ar diagenetic ages of the mixed-layer minerals suggest an illitization age of 370 to 420 Ma that agrees with the latest phase of the Caledonian orogeny. Illitization of the Kinnekulle bentonite was probably driven by the intrusion of K-rich fluids.

On treatment with dodecylammonium chloride, a synthetic Na-saturated phyllomanganate undergoes a cation-exchange reaction in which the structure expands from a collapsed basal spacing of 7 Å or a hydrated one of 10 Å to ∼ 25·5 Å. The exchange reaction is strongly influenced by the saturating cation in the original manganate and by the degree of hydration of the interlayer zone in which the exchangeable cations are located. Of the 12 cations tested, from Groups IA, IIA and IIB of the Periodic Table, only Co-manganate undergoes alkylammonium exchange when fully-dehydrated by evacuation. The results are discussed in the context of existing knowledge of the synthetic phyllomanganate and, by extrapolation, the potential value of the technique in the characterization of natural manganates has been assessed.

The effects of cobalt ions on the precipitation of goethite in highly alkaline media were monitored using X-ray diffraction (XRD), Mössbauer, Fourier transform infrared (FTIR) and energy dispersive X-ray (EDS) spectroscopies and field emission scanning electron microscopy (FESEM) techniques. Tetramethylammonium hydroxide was used as a precipitating agent. The precipitates were collected after heating of the precipitation systems at 160ºC for 2 h. The XRD results showed the formation of goethite structure as a single phase up to r = 6.98 (where r = 100·[Co]/([Co]+[Fe])). Cobalt ferrite was found as an additional phase in the precipitates obtained at r = 9.09 and 13.04. Mössbauer spectroscopy showed the formation of solid solutions of α-(Fe,Co)OOH. The incorporation of cobalt ions into the goethite crystal structure was monitored by a decrease in the average hyperfine magnetic field (⟨Bhf⟩). The value ⟨Bhf⟩ decreased linearly up to r = 5.66, whereas a nonlinear dependence was obtained at r = 6.98 to 13.04. Infrared (IR) bands corresponding to the bending vibrations δOH and γOH were shifted from 892 to 903 cm–1 and from 797 to 800 cm–1, respectively, up to r = 6.98. Fourier transform infrared spectroscopy lacked the sensitivity to monitor the effects of cobalt ions, demonstrated by the Mössbauer analysis. Cobalt incorporation into the crystal structure of goethite induced a gradual elongation of α-(Fe,Co)OOH particles along the crystallographic c axis. The formation of α-(Fe,Co)OOH nanowires was shown at r ⩾6.98. These nanowires were ~700 nm long, whereas their diameter was ~15–20 nm. The majority of the cobalt ferrite particles were in the nanosize range, as observed by FE-SEM. On the basis of the Co/Fe ratio measured by EDS, it appears that the cobalt ferrite particles were not fully stoichiometric.

The occurrence of smectite-illite and smectite-chlorite minerals series was studied along a thick clay cap (~300 m) drilled in the Cerro Pabellón geothermal field (northern Andes, Chile). X-ray diffraction (XRD) and scanning electronic microscopy (SEM) were used to characterize the alteration mineralogy and clay mineral assemblages and their changes with depth. Cerro Pabellón is a high-enthalpy blind geothermal system, with a reservoir zone from ~500 m to 2000 m depth, with temperatures of 200–250°C. Three main hydrothermal alteration zones were identified: (1) argillic; (2) sub-propylitic, and (3) propylitic, with variable amounts of smectite, illite-smectite, chlorite-smectite, mixed-layer chlorite-corrensite, illite and chlorite appearing in the groundmass and filling amygdales and veinlets. Chemical and XRD data of smectites, I-S and illites show, with some exceptions, a progressive illitization with depth. The evolution of I-S with depth, shows a sigmoidal variation in the percentage of illite layers, with the conversion of smectite to R1 I-S at ~180–185°C. These temperatures are greater than those reported for other similar geothermal fields and might indicate, at least in part, the efficiency of the clay cap in terms of restricting the circulation of hydrothermal fluids in low-permeability rocks. Our results highlight the importance of a better understanding of clay-mineral evolution in active geothermal systems, not only as a direct (or indirect) way to control temperature evolution, but also as a control on permeability/porosity efficiency of the clay cap.

Cation exchange capacity (c.e.c.) determined by methylene blue can be regarded as a useful soil mechanical test in its own right. When a large number of liquid limit (LL) tests have to be done to determine variation in clays of the same general type, as on an engineering site, economy of operation could be achieved by carrying out many c.e.c. tests and few LL tests. It is only when comparing clays of widely different types that correlation is poor.

Bottom sediments from 78 sites in the Skagerrak-Kattegat area have been used to determine the semi-quantitative distribution of clay minerals, and to interpret sediment provenance and the transport pathways. The sediment reflects incorporation of four sources, affected both by earlier glacial processes and on-going marine mixing. The southern North Sea, characterized by dioctaheadral illite, kaolinite and smectite, is the dominating source. The central North Sea provides a limited, but significant, source for chlorite. The sediment from the Swedish west coast has an unweathered character, containing trioctaheadral illite, vermiculite, illite-vermiculite mixed-layer minerals and chlorite. The contribution from the southern Kattegat (southern Sweden and Denmark) is dominated by kaolinite and smectite. Correlation between clay content and the contents of smectite, kaolinite and chlorite in the Skagerrak indicate that the clay mineral distribution is influenced by sorting. This grain-size dependency must be considered when interpreting sources.

Smectites from the E horizon of podzols dated at 1200–10,000 y in central and northern Finland were studied. Clay minerals in the fine (<0.1 μm) and coarse (0.1–2 μm) fractions were examined by X-ray diffraction. The distribution (octahedral or tetrahedral) and magnitude of the layer charge of expandable minerals were estimated using intercalation of alkylammonium ions (nC = 12) associated with the Hofmann & Klemen effect. In addition, charge alteration following desaturation (H+ exchange) and autotransformation was investigated. Smectites from the E horizons of podzols are not homogeneous but constitute a mixture of several populations with various layer charges. Smectites with lower layer charge are present in podzols having a longer effective time of pedogenesis, suggesting alteration of the high-charge smectites with time. Experimental alteration of the smectites by autotransformation shows that a decrease of the layer charge is easily produced by desaturation of the smectite clays.

Diagenetic alteration in two tuff horizons (the lower and upper tuff units) in the GoÈrdes region of Turkey led to the formation of mainly heulandite-clinoptilolite-type zeolites and also clay and silica minerals and K-feldspar. Possible variations in the climate and geological environment followed by variations in the hydrological system and the composition of the Miocene lake water and groundwater at that time resulted in the mineralogical facies. The lower tuffs are unaltered or slightly altered in the northern part and are more altered, particularly to zeolite (clinoptilolite) in the southern part of the study area. Heulandite and K-feldspar are mainly authigenic minerals in the upper tuff unit. The ammonium-exchange capacities of the 16 samples were investigated to understand the effects of the mineralogical composition on their ion-exchange capacities, which vary in the range 0.19-2.00 mEq/g. It is observed that the ion-exchange capacities are strongly dependent on the zeolite contents of the rocks. The correlation coefficient of this linear relation is 0.86. The most significant increase in ammonium-exchange capacity (from 0.2 to ~1.0 mEq/g) was observed when the zeolite contents increased from 0 to 30 wt.%. The second increase in exchange capacity was observed for samples containing >80 wt.% zeolite. Although there is no significant effect from the other authigenic minerals, smectite has a positive effect, and K-feldspar and opal-CT have almost no effect on the ion exchange capacities.

A series of reduced-charge montmorillonites with cation exchange capacities of 89, 73, 49 and 29% of the starting mineral was prepared from a Li-saturated smectite (Kriva Palanka, Republic of Macedonia) by heating at 110, 130, 160 and 300°C for 24 h (samples KP110 – KP300, respectively). Hydration properties of this series were investigated gravimetrically and by in situ XRD at different relative humidities (RHs). In the gravimetric experiments, higher water contents were observed for desorption than for sorption and hysteresis was present over the whole range of RHs for all the samples. The parent montmorillonite and the samples KP110 and KP130 retained similar amounts of water under the same conditions, thus showing that the decreased negative charge on the layers had minor effect on the water uptake at all investigated RHs. Significantly decreased water content was retained by KP160 while KP300 contained only 8% water at 100% RH. The d001 values of the parent montmorillonite and the samples KP110 and KP130 increased with RH, while those of KP160 and KP300 were independent of RH and remained at ∼10.4 and ∼9.6 Å, respectively.

The present occurrence is the only deposit among those found in Eskişehir province containing both sepiolite and palygorskite in economic amounts. To describe the geology, mineralogy and genetic relationships, two representative measured sections were examined by field work and XRD, XRF and SEM analyses. Sepiolite and palygorskite occur in a ∼40 m thick part of Pliocene sequence where saponite is also found. These minerals appear in ascending order as: palygorskite, saponite, saponite + palygorskite, sepiolite and sepiolite + palygorskite, frequently in association with dolomite. Chemical precipitation from the alkaline lake environment under semiarid or arid conditions was the main process resulting in sepiolite, palygorskite and saponite formation. Of these, saponite and palygorskite were formed when the lake water was rich-in Al and Fe. Changes in pH may have controlled whether saponite or palygorskite could be formed. Palygorskite was also developed by transformation from saponite during diagenesis.

This study focused on the structure and physical properties of acid-treated bentonite L45 from the Lieskovec deposit (Slovakia). New applications of near infrared and visible spectroscopies were used to follow Fe-montmorillonite dissolution and layer-charge reduction. Progressive dissolution of L45 results in the formation of a protonated amorphous silica phase. The OH overtone at 7312 cm–1 revealed the creation of Si–OH groups in the mildly treated samples. The area of the Si–O–Moct band, as obtained by a peak-fitting procedure, is a sensitive indicator of the changes in the octahedral sheets. Ultraviolet-visible (UV-VIS) spectroscopy of the smectite dispersions with methylene blue (MB) is an efficient method for controlling the acid activation process of bentonites. The results reveal that acid treatment causes a substantial layer-charge reduction, probably due to prevailing dissolution of MgO4(OH)2 polyhedra in the octahedral sheets. The layer-charge reduction is proportional to the structural changes and to the extent of mineral decomposition upon acid treatment.