A bentonite sample from the Petreş ti deposit, Cluj County (Romania), was used to remove heavy-metal ions (Cd2+, Pb2+, Cr3+) from wastewaters. A representative sample of bentonite (P) was characterized using the Brunauer-Emmett-Teller (BET) method, wet chemical analyses, X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The bentonite deposit from Petreş ti is present at the contact between Upper Jurassic limestones and basaltic andesites with subordinate basalt bodies. These rocks are composed of clay minerals (mainly smectite), with opal, quartz, feldspar and mica/illite as minor phases. The bentonite sample was used in powdered form (d < 0.2 mm) without any chemical treatment. The influence of the working regime, static and dynamic, on the process efficiency was studied using monocomponent synthetic wastewaters containing Cd, Pb and Cr ions. The bentonite sample proved to be efficient for the removal of these heavy-metal ions; removal efficiencies up to 100% (lead removal) were achieved.

Four drill cores along a lateritic hill in Nkamouna-Kongo (southeast Cameroon) were studied using microprobe analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The main objective of the study was to investigate the occurrence of clay silicates while evaluating the Ni-Co content of the laterite for potential mineral exploitation. The thick lateritic profiles (>40 m deep) developed on serpentinized ultramafic rocks have an Fe-rich clayey fraction, with goethite as the main mineralogical constituent and secondary quartz and relicts of magnetite-maghemite as accessory minerals. Silicate clays are less abundant and occur mainly towards the top of the profiles. At the summit of the interfluve, kaolinite and some gibbsite are associated with goethite. Along the slopes, at the bottom of profiles, the weathered bedrock shows the presence of smectite (Fe-beidellite) and kaolinite, probably due to slower water-flow conditions. Towards the top of the profile in the lower clay, ferruginous and upper clay horizons, only kaolinite remains with gibbsite, after the leaching of silica and soluble cations following repeated remobilization-recrystallization processes. At the summit, where the downward movement of water is rapid, no smectite was identified. As a whole, the mineralogical composition of the material varies in close relationship with the drainage, leading to a contrasted clay mineralogy marked by the presence of Fe-beidellite and kaolinite at the bottom, and that of kaolinite and gibbsite at the summit of the profiles.

The conductivity of La-montmorillonite was measured in the domain of water relative pressures (p/p0) of <1, and compared with the conductivites of Li- and Na-montmorillonite. La-montmorillonite shows smaller conductivity over the whole range of p/p0 studied. To explain this, theoretical considerations of the polarizing power and of the local stacking order induced by the exchangeable cation were addressed.

The potassium pools of five major physiographic units of the Urmia region situated in western Azerbaijan province, north-west Iran, were studied to determine the distribution of K forms as functions of clay mineralogy and physiographic units. Soil samples from horizons of ten pedons were selected and analysed for physiochemical properties, clay mineralogy and forms of K. X-ray diffraction patterns revealed that the soils were similar in clay-mineral compositions, consisting of illite, smectite, chlorite, and kaolinite, for the different physiographic units, but vary in the relative amounts of these minerals. The illite content was highest in piedmont plain (P.P) followed by plateau (Pl), river alluvial plain (R.A.P), colluvial alluvial plain (C.A.R) and lowland (L.L) units. Smectite content was highest in Pl followed by P.P, L.L, R.A.P and C.A.P units. Several processes, such as the diversity of weathering rate, biocyclying processes of K accumulation, geomorphologic conditions and soil formation processes, caused significant differences in most K forms in the soils. A wide variation in total K (HF-extractable K) (0.54–1.1%), non-exchangeable K (280–450 mg kg–1) and exchangeable K (217–330 mg kg–1) occurred among the physiographic units, corresponding to variations in their mineralogical compositions, mainly the abundance of illite. Significant differences (P ⩽ 0.05) were found for K, HNO3-extractable K and non-exchangeable K between the soils with large illite contents (30–50%) and with small illite contents (10–30%). A significant positive relationship existed between mineral K and illite content (r2 = 0.85, P ⩽ 0.001) and non-exchangeable K and illite content (r2 = 0.84, P ⩽ 0.001). The results indicated that these pools of K are mainly released from the frayed edges and wedge zones of illite.

A long-standing unresolved puzzle related to the Danish temperate humid climate is the presence of extended areas with large Fe contents, where goethite and ferrihydrite are present in the topsoil along with hematite and maghemite. Hematite and, particularly, maghemite would normally be interpreted as the result of high temperature as found after forest fires. However, a body of evidence argues against these sites having been exposed to fire. In an attempt to get closer to an explanation of this Fe mineralogy, an experimental forest fire was produced. The results showed a clear mineralogical zonation down to 10 cm depth. This was not observed at the natural sites, which contained a mixture of goethite/ferrihydrite, hematite and maghemite down to 20 cm depth. The experimental forest fire left charcoal and ashes at the topsoil, produced high pH and decreased organic matter content, all of which is in contrast to the natural sites. The conclusion from this work is that the mineralogy of these sites is not consistent with exposure to forest fire, but may instead result from long-term transformation in a reducing environment, possibly involving microbiology.

The Taşoluk kaolinite deposits of Afyonkarahisar (western Anatolia) are hosted by both pre-Early Cambrian sericitic mica-chlorite schists and Neogene volcanites, the latter comprising tuffs and agglomerates. These units have been affected by hydrothermal alteration controlled by faults resulting in complex, irregular, lateral mineralogical zonation. The occurrence of a siliceous cap on altered schists and in claystone, of quartz veins in schists and tuffs, and the development of explosion cones and pit fillings indicate that alteration in both the schists and the volcanites is due to hydrothermal processes. Altered schists have generally large (locally small) Fe contents, and claystones are generally silicified and have small Fe contents. Kaolinite predominates south and west of Taşoluk, whereas high (Fe+Ti)-bearing illite + kaolinite predominate in other altered sections. The kaolinite exhibits a stacked micromorphology within altered schists, and the altered volcanites record in situ precipitation, derived from a mechanism of paired dissolution and precipitation. Illite fibres coexist with kaolinite, smectite, chlorite, mica and sericitized feldspar in markedly altered schists, revealing that the illite formed either authigenically or by conversion of smectite to illite. A relative increase in Cr+Ni and decrease in Sr+Ba in the kaolinite deposits and their schistose host rock relative to the upper level of the kaolinite deposits and their volcanic parent rocks came about by the alteration of chlorite, mica and feldspar in the sericitic mica-chlorite schists, and feldspar, glass shards and schist fragments in the volcanites as a result of extensive faulting, fracturing and hydrothermal activity during Late Miocene-Pliocene volcanism, which contributed to the development of kaolinite deposits under acidic environmental conditions. With regard to industrial applications, the low-Fe kaolinized schists are suitable for use in refractories and paper coatings, while the claystone is suitable for use in ceramics and in the white-cement industry.

Development of the Polish ceramic industry over the last ten years has resulted in a sharp increase in demand for basic raw materials, especially for ceramic clays – both white- and light-firing as well as red-firing varieties. Polish sources of white-firing clays are rather scarce. Their production is based on Santonian sandy-clayey sediments of the North-Sudetic Trough (Lower Silesia, SW Poland). Light-firing varieties occur mainly in Lower Jurassic sediments on the northern margin of the Holy Cross Mountains (central Poland). Red-firing well-sintering clays of Triassic age are known in the northern margin of the Holy Cross Mountains as well as in the Cracow-Silesian Monocline.

The white-firing Santonian clays contain mainly highly-ordered kaolinite (~50%) and quartz (~30%) with minor amounts of illite. Their grain-size median ranges between 1.9 and 2.5 μm. They show moderate plasticity (bending strength after drying at 1.7–1.9 MPa) and weak sinterability (water absorption after firing ~12%), but greater lightness after firing (L parameter ~86%). The light-firing Jurassic clays are kaolinitic-illitic in character, with a variable content of quartz. Kaolinite is represented by the low-ordered variety. The grain-size median is also variable, ranging between 1.1 and 3.4 μm. They show good plasticity (bending strength after drying 2.6–2.8 MPa), good or very good sinterability (water absorption after firing <6%) but moderate lightness (L ~79%).

Triassic red clays are highly polymineralic, with illite, kaolinite, smectite, chlorite and mixed-layered minerals occurring in variable amounts. Their specific features are: large hematite content (5–12%), commonly small CaO content (<0.5 wt.%) and an extremely small organic matter content (⩽0.1 wt.%). Their grain-size median usually varies between 2 and 3 mm. Using such clays, sintered ceramics (e.g. stoneware tiles) are obtained after firing in the temperature range 1150–1200ºC.

There are numerous bentonite deposits, formed by the alteration of volcanic rocks, in the Kapıkaya area (Eskişehir, western Turkey). These deposits can be classified into three groups according to their stratigraphical levels. X-ray diffraction (XRD), scanning electron microscope (SEM), major, rare-earth and trace-element analyses of bentonites and their parent rocks from the Kapıkaya area were used to evaluate the mineralogical and geochemical properties of bentonites and their parental affinities. Mineral assemblages resulting from bentonite deposits consist mostly of clay minerals, gypsum, cristobalite/opal-CT, quartz, feldspar, calcite and dolomite. The clay minerals are represented mainly by dioctahedral smectite and lesser amounts of illite and chlorite. The enrichment and depletion of the elements indicates open-system alteration conditions. The enrichments in MgO, Fe2O3, TiO2, Co, Pb, Zn, and Ni are related to the precipitation of hydrothermal solutions channelled throughout ultramafic sources. The main differences in mineralogy and geochemistry of bentonites from the Kapıkaya area are in the smectite composition and the contents of major, rare-earth and other trace elements. The data obtained show that the types of parent rock the influenced the mineralogical and geochemical compositions of the bentonites.

Two kaolins containing kaolinites of different crystallinity, as confirmed by the Aparicio-Galán-Ferrell index, were treated in HCl and KOH solutions at 95º and 80ºC, respectively, for periods up to 36 h. Changes resulting from the treatments have been characterized by several methods. Fe occurs in the octahedral sheets of both kaolinites and dissolves similarly to Al. Lower structural ordering, more structural defects and particles of smaller average size and less regular shape are responsible for faster dissolution of KGa-2 in comparison to well ordered Gold Field (Tanzania) kaolinite. More Si than Al is dissolved in KOH from both kaolins after any dissolution time. An aluminosilicate (feldspathoid) phase is thought to occur in the material prepared from KGa-2 in KOH. Near-IR spectra provide very useful information on changes in the mineral structure upon the treatments, on the solid reaction products and on the adsorbed water molecules.

Mixed-layer illite-smectite samples from the Ordovician and Silurian K-bentonites of the Baltic Basin and the Baltic Shield (Norway, Sweden, Denmark, Poland and Estonia) were dated by K-Ar on several grain fractions and were studied by X-ray diffraction (XRD), both on oriented and random preparations, in order to reveal the conditions of smectite illitization in the area. Authigenic K-feldspar was also dated. The geographic pattern of the degree of illitization (% smectite in illite-smectite measured by XRD) is consistent with other indicators of palaeotemperatures (acritarchs, conodont alteration index, vitrinite reflectance, apatite fission track ages). It reveals the highest maximum palaeotemperatures (up to at least 200ºC) along the Norwegian and the German-Polish branches of the Caledonides and the lowest palaeotemperatures (120ºC) in the central part of the studied area. The distribution of K-Ar ages is not well correlated with this pattern, revealing a zone of older ages (Lower Devonian-Lower Carboniferous) between Denmark and Estonia, and areas of younger ages (Upper Devonian to Carboniferous/Permian boundary) to the north and south of this zone. The zone of older ages is interpreted as the result of illitization induced by a thermal event in front of the Caledonian orogenic belt (migration of hot metamorphic fluids?). The areas of younger ages are considered as representing deep burial illitization under a thick Silurian-Carboniferous sedimentary cover, perhaps augmented by a tectonic load. The K-Ar dates invalidate the hypothesis of a long-lasting low-temperature illitization as the mechanism of formation of the Estonian Palaeozoic illite-smectite. The ammonium content of illite-smectite from the Baltic K-bentonites reflects the proximity of organic-rich source rocks that underwent thermal alteration at the time of illite crystallization.

The anion adsorption capability of clays can be improved significantly by modification with certain organic cations. However, surface properties and the microstructure of the clay might change and limit the use of organo-clays in barrier systems. In this study an experimental setup is introduced which allows the rapid determination of effective diffusion coefficients (Deff) for H2O in clay samples. H2O→D2O exchange experiments on hexadecyl-pyridinium (HDPy)-montmorillonite samples were performed in a diffusion cell attached to the ATR unit of a Fourier-transform infrared spectrometer. The mean Deff for H2O in a D2O-saturated original montmorillonite is 2.44 × 10–11 m2/s in the bulk density range of 1.1–1.8 g/cm3. Hydrophobic surfaces increase the diffusivity only at high bulk densities in the saturated state. The mean Deff is lower when HDPy is applied in amounts ⩾80% of the cation exchange capacity in comparison with the original sample. At a saturation degree of the pores of 40%, Deff for all samples is one order of magnitude less than in the saturated state. Results on Deff obtained by ATR-FTIR spectroscopy are in good agreement with through-diffusion studies.

Acid mine-drainage from an abandoned Cu-S mine adit, located in the Avoca–Avonmore catchment in the southeast of Ireland, results in low-value ochre deposition. Ochre found on-site had similar physical (particle size 97.7% <2 mm and dry bulk density 0.8 g cm3), but dissimilar maximum P-retention characteristics (16–21 g P kg–1) to coal-mining ochre found in the UK. Stereomicroscopy identified oolites and diatoms in the ochre that were indicative of acidic environments. X-ray diffraction showed Fe mineralogy consisting of goethite, jarosite and minor amounts of ferrihydrite. Investigations by inductively coupled plasma-mass spectrometry and bulk energy-dispersive spectroscopy showed potentially toxic concentrations of Fe, Zn, Pb, As and Cu. Rapid mobilization of metals occurred during P-adsorption tests, which makes Avoca ochre unsuitable for use in a surface-water environmental technology.

L-cysteine (Cys) was adsorbed by bentonite (Ben) from aqueous solutions of variable concentrations and pHs. The raw materials and the adsorbed molecules (Ben-Cys) were characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermal analysis methods (TG, DTG and DSC). The results indicated that the adsorption process depended strongly on pH, temperature and concentration of amino acid. Cysteine is specifically adsorbed on bentonite surface sites, probably through its NH3+ moiety. The pH dependence suggests that these sites may be silanolate groups (≡Si-O–). It is presumed that ion exchange interaction governs the adsorption process. The experimental data of adsorption isotherms obtained and analysed with the Langmuir model showed that this model fitted the adsorption data. Calculated thermodynamic parameters (ΔHº, ΔSº, and ΔGº) indicate that the adsorption processes were exothermic.

The main physico-chemical properties of a new smectitic clay containing large amounts of amorphous material are reviewed and potential industrial applications of this type of clay are discussed. Due to a 34% amorphous material content (natural silica gel), the investigated clay has very high porosity and can be used as it is or in acid-impregnated form for oil bleaching or phosphate reduction in edible oil. In the field of biodiesel purification, the new clay can be used to remove, in particular, mono-, diglycerides and glycerol. The natural silica-smectite mixture is also suitable as a carrier for liquid ingredients, for example in animal feeds, and might serve as a partial or complete substitute for synthetic precipitated silicas. In the field of bioseparation processes, the clay can be used as an adsorbent for protein separation by means of cation exchange. Due to the suppressed swelling (compared with smectite alone), it can be packed in columns which can be regenerated.

The CRP-3 drilling project collected sediments from 3 to 939 mbsf (metres below sea floor) in the Victoria Land Basin in Antarctica. The upper sequence (down to ~790 m bsf) is of Cenozoic age and made up of detrital glaciogenic sediments; the characteristics of clay minerals in this part have been reported elsewhere. Here, the compositional features of clay minerals in the lower sequence such as conglomerates, Devonian sandstones and dolerites are described and genetic processes clarified. Clay minerals in the deepest part of the sequence derive from the alteration of different lithologies that mostly make up the sedimentary basin.

Two clay mineral assemblages were characterized through analysis by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). From 790 to 823 mbsf, samples consist of authigenic smectite of variable chemical composition forming imbricated texture of plates or flakes. The smectites probably result from hydrothermal/diagenetic transformation of earlier minerals. The primary smectite cement underwent reorganization during shearing and cataclasis. The lowest part of the sequence (below 823 mbsf) is characterized by an assemblage of kaolinite, mixed-layer illite-smectite, Fe oxyhydroxide, sporadic smectite and poorly crystallized illite. It reflects a stronger alteration process than that recorded in the upper units of core CRP-3, related to hydrothermalism connected with the intrusion of an igneous body. Both assemblages show clear differences in particle morphology, texture and smectite composition to the clay assemblages found in the Cenozoic glaciomarine sediments in the upper sequence. The different phases of alteration appear related to the processes of rifting, exhumation and faulting that characterized this region since the Mesozoic.

In this study, a new procedure for the synthesis of pillared clays is proposed. Ageing processes and intercalation reactions were carried out using microwave irradiation in order to decrease the consumption of three industrially-important parameters; time, water consumption and energy. The effects of microwave irradiation, the amount of Al and the Al3+/clay ratio on the physicochemical properties of Al-pillared montmorillonites were investigated. The structural changes, depending on the intercalation and microwave irradiation, were characterized using X-ray diffraction (XRD), Fourier-transform infrared (FTIR) and scanning electron microscopy (SEM) analyses and by measuring the specific surface area and pore-size distribution. Additionally, simultaneous thermal analyses (STA) and zeta potential measurements were carried out to determine physicochemical properties. According to the XRD measurements, the d001 value of microwave-irradiated samples is not affected by the amount of Al and the Al3+/clay ratio; microwave irradiation causes a 0.20 nm contraction in the d001 value in comparison to that of a conventionally pillared sample. The results of FTIR analyses reveal that the intensity of peaks assigned to Keggin-OH and Keggin-H2O stretches is diminished in the case of microwave-irradiated samples. The STA analyses indicate that the amount of water released during dehydroxylation is decreased in the case of microwave-irradiated samples. By considering the contraction in d001 values and the decreases in Keggin-stretching bands and also in the amount of dehydroxylation water, it was concluded that microwave irradiation has a calcination effect.

Adsorption of cis-2-butene and trans-2-butene on clinoptilolite-rich tuff and ion-exchanged forms was investigated. Clinoptilolite samples were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, chemical analysis and nitrogen adsorption techniques. Adsorption isotherms for cis and trans 2-butene on purified clinoptilolite (Cp) and modified forms (Na-Cp, K-Cp, Ca-Cp and Mg-Cp) were obtained at pressures up to 2.7 atm. and at 25ºC. The results show that natural clinoptilolite has a considerable potential for separation of the two hydrocarbons. Mg-Cp samples showed maximal uptake of both cis-2-butene and trans-2-butene.

The literature on the formation, structure and properties of allophane and imogolite is reviewed, with particular emphasis on the seminal contributions by Colin Farmer. Allophane and imogolite occur not only in volcanic-ash soils but also in other environments. The conditions required for the precipitation of allophane and imogolite are discussed. These include pH, availability of Al and Si, rainfall, leaching regime, and reactions with organic matter. Because of their excellent water storage and physical properties, allophanic soils can accumulate large amounts of biomass. In areas of high rainfall, these soils often occur under rain forest, and the soil organic matter derived from the forest biomass is stabilized by allophane and aluminium ions. Thus the turnover of soil organicmatter in allophanicsoils is slower than that in non-allophanicsoils. The organic matter appears to be derived from the microbial by-products of the plant material rather than from the plant material itself. The growth of young forests may be limited by nitrogen supply but growth of older forests tends to be P limited. Phosphorus is recycled through both inorganic and organic pathways, but it is also strongly sorbed by Al compounds including allophane. When crops are grown in allophanic soils, large amounts of labile P are required and, accordingly, these soils have to be managed to counteract the large P sorption capacity of allophane and other Al compounds, and to ensure an adequate supply of labile P. Because of their physical and chemical properties, allophanic soils are excellent filters of heavy metals and pathogens.