A near infrared (NIR) spectroscopy approach was undertaken to collect information on the Al cationic distribution in tetrahedral and octahedral sites in natural chlorite (clinochlore) samples. Structural formulae were established using electron microprobe and Mössbauer spectroscopy. A band located near 7115 cm–1 was attributed to the overtone of OH fundamental stretching mode of Mg2AlOH and increases with the total Al amount. Good correlation was obtained between the (SiAl)O–OH vibration band area and tetrahedral Al content, making it easy to partition Al (and thus Fe3+) between octahedral and tetrahedral sites.

Four different types of natural clay were tested as potential adsorbents for toxic Pb2+ ions. Based on the preliminary screening studies, the adsorbents were effective at retaining Pb2+ ions from solution. A strong correlation was observed between the cation exchange capacity of clay samples and their function as adsorbents of Pb2+ ions. An adsorption isotherm of Pb ions on Petra clay was measured at 30ºC and at a concentration range of 0 –200 mg dm–3. Over the entire concentration range, the Langmuir isotherm gave a good representation of adsorption data, which confirms the formation of one molecular layer of adsorbate on the clay surface. Two variables were investigated to elucidate the rate-limiting steps of adsorption: the effect of initial concentration of Pb2+ and the effect of solution temperature. It is concluded that external diffusion was the only mechanism in operation in the adsorption process. It has been noted that adsorption of Pb2+ by natural clay is a fast process, where 80% of equilibrium capacity was established within the first minutes of interaction.

FTIR spectroscopy has been applied to NH4+-exchanged dioctahedral clay minerals to determine the molecular environment of NH4+ and to quantify N concentration. FTIR under vapourpressure control, coupled with heating and freezing treatments has shown that NH4+ ion symmetry varies with the nature of clay minerals. NH4+ has a perfect tetrahedral symmetry in hydrated or dehydrated smectites and belongs to the Td symmetry group. The NH4+-bending vibration is centred at 1450 and 1425 cm–1.

The Si4+-Al3+ substitution in dioctahedral clay minerals induces the loss of symmetry elements of the NH4+ tetrahedron which acquires a C2v symmetry. As a consequence, the Td –C2v transition can be used to characterize the smectite–illite transition. Quantification of NH4+ content per half unit cell is provided by nNH4 = k[NH4]/[OH] where [NH4]/[OH] is the band area ratio of the NH4+-bending vibration to the OH-stretching vibration. k = 1.1 for hydrated smectite, 0.9 for dehydrated smectite and 0.8 for illite or tobelite. The bending vibration of NH4+ is chosen for the calculation because it is not affected by superimposed contributions.

29Si, 27Al MAS NMR is used to characterize Laponite RD and synthetic saponites of variable interlayer charge. The Si/Al ratios are in good agreement with the calculated charge from chemical analysis except for the lowest-charged saponite. In contrast to the 29Si MAS NMR spectra in which resolved signals are detected, the 27Al MAS NMR spectra show one signal whose linewidth increases with the clay charge. The water content of the clay samples was obtained from 1H MAS NMR.

The 2D MQMAS NMR technique is required to obtain a high-resolution spectrum of nuclei with strong quadrupolar interaction. This method was applied to the 23Na nucleus of clay counterions and to the 27Al structural nucleus. One well-defined 23Na NMR signal is observed for all the clays studied except the highest-charged saponite. Possible explanations for this different behaviour are discussed. The calculated isotropic chemical shift evolves progressively with the clay charge whereas the deduced quadrupolar interaction does not change significantly. The 27Al 2D 3QMAS technique was not able to resolve more than one signal.

The clay mineralogy of soils and of the main calcareous sedimentary parent rocks of southern Iran were investigated to determine their origin and factors controlling their distribution pattern in soils. The results revealed that the soil-available moisture plays the major role in the distribution pattern of palygorskite and smectite clay minerals in the arid and semi-arid areas studied. There is an inverse correlation between palygorskite and smectite with regard to the soil-available moisture as expressed by P/ETº (ratio of mean annual precipitation to mean annual reference crop evapotranspiration). At P/ETº values >0.4 palygorskite transforms to smectite. Smectite is thought to be mainly of ‘transformed’ origin. It is detected in trace amounts in soils of more arid areas and increases in soils having greater available moisture. The general decrease in illite content with depth is related mainly to its transformation to smectite under favourable moisture conditions of the deeper horizons. Palygorskite is considered to be inherited in plateau soils of the arid regions whereas in saline and alkaline soils and soils with high gypsum, it is mainly of authigenic origin. The P/ETº and gypsum content show a significant correlation with the palygorskite content. The occurrence of kaolinite in some soils is due to its inheritance from the surrounding kaolinite-bearing Cretaceous rocks. Illite and chlorite abundance in soils is also largely related to their presence in parent rocks. The rare occurrence of vermiculite in the studied calcareous soils is mainly related to its lower stability under high pH, low Al activity and the presence of large amounts of Si and Mg in soils.

Purified kaolins from Thai soil on diverse parent materials were characterized using analytical transmission electon microscopy, X-ray diffraction, thermogravimetric analysis and chemical analysis. The properties of Thai soil kaolins appear to be more diverse than Indonesian and Western Australian soil kaolins investigated using the same analytical procedures; this difference may reflect the greater range of parent materials for the Thai soils. The kaolins show a variety of crystal morphologies including euhedral hexagonal to subhedral platy crystals, tubes and laths and several morphologies were present in most samples. TEM-EDS enabled analysis of single crystals of each morphology present within a sample. Tubular or lath-shaped crystals usually have lower %Fe2O3 contents than hexagonal platy crystals in the same sample. The relationships between crystal size and Fe content within morphological populations were also examined by TEM-EDS. Generally, smaller kaolin crystals display a wider range of Fe concentration than the larger kaolin crystals in the same sample. Increasing Fe concentration in bulk samples is closely correlated to decreasing coherently scattering domain size (R2 = 0.57), increasing cation exchange capacity (R2 = 0.44) and increasing specific surface area (R2 = 0.65). However the properties of the deferrated soil kaolins, including their Fe content, are not related to forms of Fe, (total Fe, amorphous or organic) in the untreated clay fraction of the soil.

Inhibited vermiculite is a common minor constituent of these clay fractions and its average structural formula derived from EDS data indicates that it was formed by Al replacing K in muscovite. One Al3+ ion occupies the interlayer space previously occupied by three K+ ions. As the distances between these Al3+ cations in the interlayer space is large it is proposed that isolated or loosely associated hydrated Al3+ groups such as Al(OH2)63+ exist that resist exchange by other cations due to hydrogen bonding with the adjacent tetrahedral oxygen surfaces

The evolution of textural properties of Na/Ca-bentonite from Wyoming (MX-80) was studied by adsorption of nitrogen, water vapour, and ethylene glycol monoethyl ether. Clay suspensions were heated at 80 and 300ºC for up to 9 months in the absence of or in the presence of Fe and/or Fe oxides. The treatment without Fe did not change the textural properties of the samples significantly. The treatment at 80ºC in the presence of Fe resulted in a considerable increase in the external surface areas of the samples. The total and external surface areas and swelling capacities of the samples decreased following the treatment at 300ºC in the presence of Fe and Fe oxides. In the case of larger additions of Fe, the treatment at 300ºC resulted in a considerable decrease in the total and external surface areas and swelling capacity of the sample and in the formation of a network of large-size pores, in which all the pores were connected.

Back-scattered scanning electron microscopy (SEM) images of Cr-chlorite crystals from Erzerum (Turkey) reveal that the crystals are chemically inhomogeneous and display complex but well defined crystal zoning characterized by growth bands with contrasting chemical features. The chemical zoning has been investigated at the micron scale using an integrated approach, combining BSEM images, in situ chemical analysis by electron microprobe and Raman spectroscopy. Enrichment in Cr, due to octahedral Al substitution, reaches up to 0.7 atoms per half formula, especially in bands where the Mg content is depleted. These substitutions are also depicted at the micron scale on Raman spectra by changes in the v(OH) band intensities and positions that correlate with the Cr content. The Cr-enrichment occurs thus during specific stages of crystal growth, probably in response to changes in the fluid chemistry controlling the relative availability of Cr, Mg and Al in solution.

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).

In the area of S° ile, NW Turkey, Upper Cretaceous calc-alkaline volcanic rocks with compositions ranging from andesite to rhyolite have been recognized. The most widespread rocks of the suite are andesites, which can be grouped into altered and fresh. The oldest altered andesites are the parent rocks for the kaolin deposits of the study area. The Upper Cretaceous volcanic suite consists of spilite, basalt, andesite, trachyandesite, trachyandesitic and hyaloandesitic dacite, rhyolite lavas, tuffs and agglomerates. The highly altered andesites are composed of plagioclase, pyroxene, hornblende, biotite, augite and very fine opaque minerals. During the Turonian, an E –W trending extensional magmatic arc was developed in the Istanbul Tectonic Zone of the oceanic Western Black Sea basin and intermediate volcanic rocks were emplaced, mostly calc-alkaline andesites, suggesting multi-stage magmatism. The significant features of the andesites are: (1) enrichment of LILE (Rb, Ba, K) over HFSE (Zr, Nb, Hf, Ti, Th, U, Y) and LREE (La –Sm), resulting in high Ba/Nb, Th/Nb, Ba/La, K/Ti and Th/La ratios; (2) depletion of LREE over HFSE, MREE and HREE, generating high La/Nb, Ce/Ti, La/Sm and La/Y values; and (3) depletion of Nb, Sr and Ti; all of which are typical of island arc magmatism, with possible back arc signature. The Th-Hf-Ta diagram for tectonomagmatic classification shows that the S° ile calc-alkaline rocks are similar to volcanic rocks from the Mariana Arc, the Aeolian Arc of Salina, Italy, the Skaros island in the Aegean Sea and Sardinia's ignimbrites. Moreover, relatively low La/Th and Ce/Pb ratios suggest that the source region of volcanism was enriched in LILE with respect to REE, indicating crustal contamination during melting.

Highly weathered andesitic rocks, rich in smectite, were transported gradually and deposited in a lacustrine basin, a coal-forming dysaerobic environment, in which they were subject to post-depositional alteration, or in situkaolinization, to form a kaolin deposit in the presence of humic and fulvic acids. The mobility of major and trace elements and REEs during the progressive kaolinization of andesitic materials has been investigated to reveal the geochemical characteristics of Upper Cretaceous volcanic parent rocks and to explain mineralogical processes in a kaolin deposit as a daughter rock ‘end-product’ . Alteration is characterized by the loss of Si, Fe, Ca, Na and K, and by the gain of Al, Ti, Zr and LOI. Moreover, Ho, Er and Yb are immobile, and Hf, Zr and Nb are mobile. Th and U are slightly enriched in clay horizons with respect to the andesitic rocks. In addition, Cr, Ga, Nb and Ta enrichments indicate variable sources of terrigenous sediments and differential mobilities of elements in lake waters rich in organic acids. The anatase concentration increases in the <2 mm size fractions as subspherical particles and these precipitate at acidic conditions (pH ≈ 5) during early diagenesis.

An ab initio determination of the structure of sepiolite after acid treatment (HCl 0.5 N for 24 h) was carried out using X-ray powder diffraction data. After acid treatment, the sections normal to the a and c axes presented discontinuities, ∼2.25 Å wide, parallel to the (010) plane, with no electronic density maxima, thus suggesting that adjacent planes are joined by van der Waals-like residual links. Partial dissolution was detected on both octahedral and tetrahedral sheets, beginning by breaking the ribbons not along the edges, but in the centre, thus creating a 5.20 x 66.79 Å tunnel along the a axis. By interrupting the tetrahedral sheet, this mechanism changes the phyllosilicate-like nature of the sepiolite to an inosilicate-like structure.

Residual clays that developed on Permian and Carboniferous glass-rich silicic volcanic rocks (pitchstones, ignimbrites) at the Seilitz and Kemmlitz kaolin deposits, Saxony, Eastern Germany, contain locally abundant lath-shaped illite-rich illite-smectite mixed-layer minerals (I-S). Analyses by XRD and TEM-AES reveal a large illite percentage (>∼90%) and R3 ordering in I-S from Seilitz (>∼90%) and smaller illite percentage (∼70%) and R1 ordering in I-S from Kemmlitz. The clays never suffered a deep burial and there is no geological, petrographic or fluid inclusion evidence for aeolian input or hydrothermal origin of I-S at either deposit. The I-S formed exclusively at the expense of volcanic glass and not from K-feldspar. Residual quartz phenocrysts in the clays still preserve primary glassy silicate melt inclusions and lack secondary aqueous fluid inclusion trails. The dD and δ18O values of kaolinite and I-S are suggestive of low formation temperatures (<40ºC). Rb-Sr and K-Ar dating of I-S-bearing clay separates yield Lower Cretaceous ages at Seilitz and indicates the presence of excess or inherited 40Ar in illite-rich I-S. In contrast, Triassic to Jurassic Rb-Sr ages are obtained for I-S from the Kemmlitz kaolin deposit.

Kaolinite cation adsorption data are processed using recent gas adsorption concepts such as the undersaturation ∆m = ln (C/Cs) and the monolayer coverage y. This process shows that using the proper reference phase through its solubility Cs, it is possible to characterize adsorption sites that have the same adsorption energy regardless of the nature of the cation. Under mildly acidic conditions, a single ‘Langmuirian’ site category fits cation adsorption data whereas another family of sites is revealed in mildly alkaline conditions. These results suggest that at mildly acidic pH, only silanol sites are available to ion exchange and adsorption whereas at higher pH, a wider range of sites is made available, some of them displaying the same average adsorption energy and the others constituting a different category of sites with a much lower adsorption energy. This latter category is attributed to the aluminol sites.

The firing transformations of a Triassic calcareous clay were investigated, in the range 800 –1075ºC, by using X-ray diffraction and by measuring some ceramic properties (linear shrinkage, density and porosity). It was found that gehlenite and wollastonite are the only neoformed crystalline phases, when anorthite is also expected. The occurrence of these phases is discussed, emphasizing the role of the activity of free silica and calcite concentration. Moreover, new reaction paths for anorthite and wollastonite are envisaged.

The thermal transformations of kaolinite have been studied using 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetric analysis (TG). The experimental results show that this sample is a pure kaolinite which contains ∼3% carbonaceous material as impurity. 27Al and 29Si MAS NMR spectra show that the microstructural evolution of the thermal transformation of kaolinite at 450 –1050ºC is similar to that of the kaolinite– mullite reaction series previously published by many authors. 29Si MAS NMR spectra of mullite at 1190 and 1250ºC display two resonances at ∼ – 87 and –92 ppm, corresponding to sillimanite-type geometry around Si and the typical Si environment of mullite, respectively. At 1350ºC, the splitting of (hk0) and (kh0) of mullite occurs, indicating that the primary mullite transforms into orthorhombic mullite. Simultaneously, the resonance at ∼ – 92 ppm splits into two signals at ∼ –90 and –94 ppm. 27Al MAS NMR spectra of the mullite consist of three signals centred at ∼ –4, 45 and 60 ppm, corresponding to octahedral, distorted tetrahedral and tetrahedral Al sites, respectively.

Microanalytical data on Plio-Pleistocene sediments from a Salton Sea Geothermal Field well define the evolution of textures and mineral assemblages from sediment to metamorphic rock in an open hydrothermal system.

At shallow depths detrital grains occur within a fine-grained matrix of I-S and illite. As depth and temperature increase, grains lose their detrital characteristics; they subsequently form a continuous intergrown array of irregular domains, with phyllosilicates occupying the progressively decreasing pore space.

Illite and chlorite are authigenic phyllosilicates down to 2500 m, where biotite occurs. Authigenic phyllosilicates occur as subhedral crystals (200 –600 Å thick). Alkali feldspar has end-member compositions, implying exchange of alkalis with convected fluids. Changes in texture imply dissolution of detrital phases and neocrystallization of authigenic phyllosilicates directly from pore fluids. Changes with depth are not time-dependent for phyllosilicates: they formed simultaneously at all depths as a result of a single hydrothermal event in an open system.

Cationic dye, methylene blue (MB), was intercalated into films of expandable clay minerals with low, moderate and high layer charges (saponite, montmorillonite and synthetic expandable mica-fluorohectorite, respectively) . Tilted orientation of the dye cations on the silicate surface was observed by polarized ultraviolet-visible (UV-Vis) transmission spectroscopy. The tilting angle of the dye cations increased with the formation of high-order H-aggregates that absorb light at 525 nm. These dye species were formed only on the surface of fluorohectorite, which has the highest layer charge, and exhibited dichroism. Models for the orientation of MB cations on a clay surface were proposed based on MB orientation models previously reported, and compared with the basal spacings determined by X-ray diffraction.

13C CP MAS NMR and 29Si MAS NMR were used to characterize silylated montmorillonites and to estimate the extent of the silylation reaction. Indirectly-detected proton relaxation times of the intercalated surfactant were measured in both silylated and non-silylated clay systems to monitor the dynamics of intercalated species. A greater degree of mobility in the silylated montmorillonites was found. The lack of NMR information resulting from paramagnetic interaction brought about by structural Fe(III) ions was considered. The resulting broadening can prevent the estimation of the trans/gauche conformer ratio of the intercalated surfactant alkyl chain.

This paper summarizes recent results obtained on chemical modifications of smectites. These include replacement of exchangeable cations with protons, a process connected with smectite autotransformation – attack of protons on the layers and liberation of central atoms from the octahedral and tetrahedral sheets, causing modification of the acid sites on the particles. More severe modifications occur during dissolution in inorganic acids, when the layers are dissolved and threedimensional amorphous silica is formed. The negative charge on the smectite layers can be increased via reduction of structural Fe(III) to Fe(II) or decreased via fixation of small exchangeable cations, such as Li+, upon treatment at elevated temperatures. Heating for 24 h at different temperatures between 100 and 300ºC leads to a series of chemically similar materials of different charge, prepared from the same parent mineral. Such series are suitable for investigation of the effect of the layer charge on selected properties of smectites. Fe(II) can be partly stabilized in reduced smectites by Li fixation upon heating.

In 1985, Dashidaira Dam, equipped with a flushing gate, was built on the Kurobe River in Toyama, Japan. Since the dam sediments were first flushed out in December 1991, benthic fish counts have decreased year by year due to repeated flushing of clay-rich dam sediments.

In June 2001, the flushed dam water contained a low oxygen concentration (1 to 2 mg/l) and high concentrations of smectite and vermiculite. To establish the cause of the death of the benthic fish, living flatfish were collected from Toyama Bay in order to examine their gills, which showed tissue damage and chemical changes caused by adherent expandable clays, derived from the flushed dam sediments. For comparison, exposure experiments on rainbow trout were carried out using smectite suspensions. Examination by optical microscopy revealed that the gills had shrunk because of the smectite concentrations. Low oxygen concentrations and large amounts of expanding clays have a significant effect on downstream benthic life.