The influence of hydrological conditions and the pH of the environment on chlorite and mica transformations in the acidic weathering zone of pyrite-bearing schists was studied. Phyllosilicate transformations were investigated in the area of the abandoned pyrite open-pit mine in Wieściszowice (Lower Silesia, SW Poland) using X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy and chemical methods. (Mg, Fe)-chlorite, micas (muscovite and paragonite), quartz, feldspars and pyrite were reported to be the most abundant minerals occurring in pyrite-bearing schists. Phyllosilicate transformations were significantly stronger in dry conditions than in wet ones. This conclusion was supported by the fact that the inherited phyllosilicates predominated in the clay mineral fraction of waterlogged saprolites, whereas the secondary swelling minerals were minor components. In dry and extremely acidic saprolites (pH < 3), trioctahedral chlorite was dissolved and transformed into clay minerals (e.g. smectite and kaolinite), whereas swelling clays (smectite mainly) were formed at the expense of dioctahedral micas. The pH of water is an important factor influencing phyllosilicate transformations in waterlogged conditions. The phyllosilicate alterations under the influence of extremely acidic waters (pH < 3) were more advanced than in moderately acidic ones (pH of 4.6), as the secondary clay minerals seemed to be represented exclusively by smectite in the former, whereas HIMs and mixed-layer minerals such as R0 I-S-Ch, R0 I-S, as well as R1 Ch-V and/or R1 Ch-S occurred in the latter.

Basalts and related magmatic rocks such as diabase are frequently used as raw materials in the building and construction industry as dimension stones or as aggregates, where they may form the sub-bases of roads or railway embankments. A major characteristic controlling the quality of the raw materials is the rock strength, which can be affected by the presence of swellable clay minerals (smectites). Increasing smectite content is generally considered to increasingly affect rock integrity. Industrial practice, in which the smectite content is monitored via cation exchange capacity (CEC) methods, on the other hand, showed that both mechanically stable smectite-rich and unstable smectite-poor materials exist. We therefore studied the CEC–strength relation based on twelve samples from a German diabase quarry.

As could be expected, the sample with the highest CEC was the least stable. However, the comparison of the rock strength with the CEC of the other samples was less clear. Comparing the CEC of powders and of the 1–2 mm fraction of the same sample provided additional information. In the case of samples which are relatively stable (in spite of high CEC values), the CEC values of the powders were significantly higher than those of the 1–2 mm fraction. Samples with less rock strength, on the other hand, showed equal CEC values of the powder and the 1–2 mm fraction. This difference may be explained by different accessibilities of the smectites for CEC exchange solutions during typical experiments.

In conclusion, the application of the CEC method for quality control considering both powdered and 1–2 mm samples allows a more precise estimation of the rock strength to be made, particularly for the comparison of different materials. Although measurement of two CEC values (after both sieving and grinding) would complicate quality control, the present study indicates that valuable additional information, i.e. semi-quantitative information on the accessibility of smectites, is gained.

The use of organoclays as adsorbents in the remediation of polluted water has been the subject of many recent studies. In the present work, a Tunisian smectite modified with two cationic surfactants was used as an adsorbent to examine the adsorption kinetics, isotherms and thermodynamic parameters of fluoride ions from aqueous solution. Various pH values, initial concentrations and temperatures have been tested. Two simplified kinetic models, first-order and pseudo-second-order, were used to predict the adsorption rate constants. It was found that the adsorption kinetics of fluoride onto modified smectites at different operating conditions can best be described by the pseudo-second-order model. Adsorption isotherms and equilibrium adsorption capacities were determined by the fitting of the experimental data to well known isotherm models including those of Langmuir and Freundlich. The results showed that the Langmuir model appears to fit the adsorption better than the Freundlich adsorption model for the adsorption of fluoride ions onto modified smectites. The equilibrium constants were used to calculate thermodynamic parameters, such as the change of free energy, enthalpy and entropy. Results of this study demonstrated the effectiveness and feasibility of organoclays for the removal of fluoride ions from aqueous solution.

The empirical application of muds for therapeutic purposes is widely known. This is called pelotherapy and consists of the local or generalized application of a mixture of a solid phase and a liquid phase (peloid) for the recovery of arthro-rheumatic issues, bone-muscle traumatic damage and dermatological pathologies. During the time of mixing (maturation process) the mud is progressively colonized by thermophilic microorganisms that contribute to improvements in the peloid quality and endow the mud with organic substances. Several studies report diatoms as the main agent of thermal muds capable of producing anti-inflammatory sulphoglycolipid which renders the mud suitable for this use. The effect of the temperature is also considered important for therapeutic purposes.

Recent studies assessed physical, chemical and technological properties of some peloids in use at spa centres. Some maturation surveys have also been performed in recent years. The need for quality criteria establishment and certification of clayey products intended to be used currently is evident, especially for peloids which have therapeutic action. Consequently, this study aims at the compilation and analysis of some characteristics of peloids from the literature in order to contribute to a major database that allows the establishment of regulations and quality criteria for suitable applications of peloids.

The exchange reaction of Na-bentonite with zirconium pillars gives products which suffer from a loss of crystallinity, with basal spacing about 18 Å and surface area of 200 m2 g–1. Aluminium introduced in different amounts in the zirconium intercalated solution leads to an improvement in the stability and crystallinity of zirconia-pillared clays (Zr-PILCs) and creates pillared clays with new properties. Adding a small amount of Al (10 molar %) leads to an increase of d001 from 18 Å to 20.5 Å and an increase of the percentage of introduced zirconium from 16.71 to 21, expressed as ZrO2 wt.%, accompanied by an increase of the Brönsted and Lewis acidic sites. The acetalization of acetone with ethylene glycol was studied in order to compare the activity of PILCs. The results show that the yield of the aforementioned reaction depends strongly of the composition and acidity of the catalyst.

The mineral stability of two bentonites was studied in the presence of pyrite concentrate to simulate the possible reactions between the bentonite barrier used in a high-level nuclear waste (HLW) repository and host rock containing up to 5 wt.% of admixed pyrite. Smectite was the only bentonite mineral affected by pyrite treatment under the experimental conditions used. Bentonites reacted differently with pyrite due to the different nature of the smectites. The distinct crystal chemistry of the smectites controlled by the composition of the parent rocks influenced the smectite surface properties (cation exchange capacity and layer charge distribution) which resulted in a different response of the bentonites to pyrite treatment. A partial transformation of the original smectites into H-smectites represented the initial stage of smectite destabilization on acid attack. Rising non-equivalent isomorphous substitution in the octahedral sheets of the smectites enhanced smectite reactivity and thus the reaction between bentonite and pyrite, causing lower stability of the bentonite containing high-charge smectite.

We have examined the nature and origin of smectites in glaciomarine sediments of the AND-2A drill core (McMurdo Sound, Antarctica) by means of X-ray diffraction (XRD) analyses on the clay fraction, field emission scanning electron microscopy (FESEM), scanning electron microscopy (SEM) observations and SEM-EDS microanalyses on smectite particles. Relying on the smectite variation throughout the drill core it was possible to split the sequence into three units. Smectites throughout the core are either detrital or authigenic. Detrital smectites are close to montmorillonite-beidellite in composition while newly-formed smectites frequently have higher Fe-Mg contents and intermediate compositions between the saponite and nontronite field, with lower amounts in the montmorillonite-beidellite field. In the upper sedimentary sections (Unit I, and Unit II, 36-440 mbsf, 0.7-16.5 Ma) smectites are interpreted to be predominantly detrital, whereas in the lower portion of the core (Unit III, 440-1123.20 mbsf, 16.5-20.2 Ma) authigenic smectites are the most common feature. The predominance of mica, the abundance of chlorite, and the nature of smectites in the upper units indicate physical weathering under cold and dry climate, and a dominant provenance for the clay minerals from the Transantarctic Mountains. Smectites in the lower unit are considered mostly authigenic and they are most likely to be the result of early diagenetic processes, being formed from the alteration of volcanic material (glass, pyroxenes and feldspars) and/or through precipitation from fluids of a possible hydrothermal origin. Our survey attests to the importance of discriminating between a detrital and authigenic nature of smectites as the occurrence of authigenic clay minerals in ancient sedimentary successions might lead to incorrect palaeoclimatic interpretations, since they can be affected by diagenetic processes, thus obliterating the climatic signal.

There is interest in exploiting and developing natural resources, particularly deposits of natural clays. Senegal has several clay mineral deposits for which chemical and mineralogical compositions have been little studied. Some of these natural materials are nowadays used in pottery and ceramics. To extend applications, a better basic knowledge is required and, for this objective, the raw clay and separated <2 μm clay fraction from Keur Saër (Senegal) were subjected to chemical and mineralogical studies. Several techniques including X-ray diffraction (XRD), thermal analysis (TG-DTA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), N2 adsorption-desorption isotherms, cation exchange capacity (CEC) measurements and solid state nuclear magnetic resonance (NMR) have been used to characterize the material. It was found that the raw clay and the separated clay fraction consist of a mineral mixture in which kaolinite is the main component. 29Si and 27Al MAS-NMR spectra show the presence of silicon atoms linked to three other silicon atoms via an oxygen atom and six coordinated Al atoms. Significant increases in the specific surface area and cation exchange capacity were observed on purification, reaching a maximum of about 73.2 m2g–1 and 9.5 meq/100 g for the separated fine clay fraction while the values for the raw material were around 28.9 m2g–1 and 7.3 meq/100 g.

Although numerous models for the formation of glauconite have been presented, the precise process and micro-environment of glauconitization are still poorly constrained. We characterize the special micromilieu of glauconitization developed during early diagenesis and present a model for glauconite formation in fecal pellets.

Glauconitization at Oker (Central Germany) occurred predominantly in fecal pellets deposited in a shallow marine-lagoonal environment during the Kimmeridgian. Within the fecal pellets, rapid oxidation of organic matter provides the post-depositional, physicochemical conditions favourable for glauconitization. Replacements of matrix calcite, dissolution of detrital quartz, K-feldspar, and clay minerals, and Fe redox reactions were observed within the early micro-environment, followed by the precipitation of euhedral pyrite, matrix-replacive dolomite, and megaquartz accompanied by I-S formation as thin section analyses and SEM observations show. Carbonate geochemical compositions based on ICP-OES and stable oxygen and carbon isotope signatures demonstrate that glauconite formation started in a suboxic environment at a pH of 7–8 and a temperature of 22±3°C to 37±2°C at maximum.

TEM-EDX-SAED and XRD analyses on separated glauconite fecal pellets and on the <2 μm clay mineral fraction reveal the predominance of authigenic 1Md-glauconite, 1Md-glauconite-smectite, and 1Mdcis-vacant I-S, besides accessory detrital 2M1-illite and montmorillonite. Kinetic modelling of the glauconite (93–94% Fe-illite layers and 6–7% Fe-smectite layers, R3) and of I-S (66–68% Al-illite layers and 32–34% Al-smectite layers, R1) leads us to conclude that the I-S formed solely by slow burial diagenesis, whereas the glauconite formed close to the seafloor, suggesting significantly faster kinetics of the glauconitization reaction compared with smectite-illitization related to burial diagenesis. Thermodynamically, the substitution of octahedral Al3+ for Fe3+ and Mg2+ during the Fe-Mg-smectite to glauconite reaction via the formation of glauconite-smectite mixed-layered clay minerals may have resulted in a higher reaction rate for this low-temperature glauconitization process.

Electron paramagnetic resonance (EPR) spectra of different particle size fractions of four kaolins from diverse sources in North America, Europe and Asia have been investigated in order to characterize their paramagnetic properties and heterogeneity. There were major differences in the sources of the EPR signals from transition metals; V and Mn were structural, Fe was both structural and as associated oxides, and Cu was in the form of an adsorbed ion. The radiation-induced free radical signals commonly known as the A- and B-centres were observed in three of the deposits; however, in addition to the previously reported 27Al hyperfine structure associated with the B-centre, we also observed much smaller 27Al hyperfine structure on the g┴ feature of the A-centre. The other kaolin sample produced four free radical signals that have not previously been reported in kaolins. Each had substantial 1H hyperfine splitting; three are interpreted as corresponding to defect centres associated with Si-OH groups, and the other to a Si hole surrounded by protonated O atoms. The EPR spectra changed progressively with particle size, and measurements on the Asian specimens after grinding showed major differences in the Fe3+ signals from the same particle size fractions separated from the natural samples, thus supporting previous reports that grinding results in major structural changes in the minerals.

The Georgia, USA, kaolins contain three major occurrences of Fe-sulphide minerals, namely (1) in burrow structures, (2) as nodules associated with lignite and (3) as finely disseminated material. We have used sulphur isotope analysis and X-ray powder diffraction to understand these three occurrences in order to gain insight into the diagenetic conditions and microbial influences affecting the kaolin mineralogy. Burrows and nodules are dominated by corroded marcasite with thin pyrite overgrowths. The δ34S composition of each sulphide sample has internal fractionations (δ34Shigh – δ34Slow) ranging from 22‰ to 67‰. The secondary pyrite phase tends to be the most 34S depleted, with a low δ34S value of –47‰, whereas marcasite displays a δ34S range from 30‰ to +33‰. Early acidic environments from organic acids could have facilitated the initial marcasite crystallization, with a pH increase during later diagenesis producing pyrite overgrowths. Sulphide formation would have continued until burial restricted the diffusion of sea-water sulphate. At this point, the metabolism of sulphate-reducing bacteria would have been retarded, producing δ34S values ranging from –30‰ (open sulphate supply) to +40‰ (highly restricted sulphate supply). Under the nutrient-starved conditions of later-diagenesis, disproportionate sulphur-reducing bacteria would likely have become more dominant, yielding additional δ34Ssulphide fractionation and producing the observed fractionation (δ34Ssulphate – δ34Ssulphide) values of +67‰.