Layered double hydroxides (LDHs) are known as ‘anionic clays’. They comprise a class of material with positively charged octahedral double hydroxyl layers and exchangeable anions. The Li/Al LDH term includes a group of LDHs with Li/Al octahedral double hydroxyl layers. We have demonstrated a modifed method, using Li/Al LDH-OH (OH− as interlayer anions) as the starting material, for preparing Li/Al LDH-X (X represents interlayer anions, including dioctyl sulphosuccinate (DOSS), dodecyl sulphate (DDS), mercaptoacetate (MA), EDTA, Tiron and dichromate) under mild acid conditions (pH in the range 4 to 5). However, in the case of acidsensitive anions, Fe(CN)64−, Li/Al LDH-Fe(CN)64− can be prepared by a two-step procedure using Li/Al LDH-DOSS or similar compounds as intermediates to react with acid-sensitive anions under mild alkaline conditions (pH ≈ 9).

China is a significant producer of kaolin with 2.1 Mt in 2002 representing 8.4% of the world's total of 24.9 Mt. The kaolin resources are widespread throughout the country and are varied in their origin, physical and chemical properties and morphology. The kaolin industry, compared to Europe and the USA, is fragmented with no single large company. In 2002, China was the world's largest producer of ceramics, particularly for sanitary ware and porcelain. Also, China is now the second largest producer of paper and paperboard in the world. The quality of kaolin and halloysite is suitable for ceramics with no need to import. However, the quality of existing paper/ board-coating clays is not up to the quality of imported material from Brazil and the USA and there is an urgent need to develop local resources to meet the present and future demands of the market.

The structure of an illite-smectite (I-S) sample (HSI) from the Tertiary–Cretaceous boundary layer at Stevns, Denmark, i.e. the so-called Fish Clay, is investigated in order to discuss the origin of this clay and its similarity to clays from Maastrichtian-Danian chalk of Denmark and the North Sea. The phase compositions and layer sequences have been determined by X-ray diffraction. The structural formulae are determined from chemical analysis and solid-state 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The octahedral vacancy pattern has been determined by thermal analysis and the particle shape by atomic force microscopy. The HSI sample I-S consists of two phases, a high-smectitic (HS) phase (70%) having 95% smectite and 5% illite (leucophyllite) layers, and a low-smectitic (LS) phase (30%) having 50% smectite and 50% illite (leucophyllite) layers. Both phases have trans-vacant dioctahedral sheets and contain only traces of IVAl, the charge of the illite (leucophyllite) layers being provided predominantly by octahedral Mg for Al substitution. The structure of the tetrahedral and octahedral sheets for the HSI are compared to the structure of an I-S sample (GRI) from the Maastrichtian chalk at Stevns below the Tertiary-Cretaceous boundary and to the standard smectite SAz-1 from Arizona. For all three samples the 27Al MAS NMR spectra show the presence of two resolved IVAl resonances, which indicate the presence of two different IVAl sites. The NMR, infrared spectroscopy and chemical data show that both HSI and GRI have highly ordered Mg for Al substitution in the octahedral sheet, each Al having one Mg and two Al neighbours, whereas substitution of Mg for Al in SAz-1 is random. For the HSI sample, both the HS and LS phases are probably formed from volcanic ash. The structural similarity of the phases in HSI and GRI shows that GRI formed from a material similar to HSI by illitization of the HS phase and chloritization of the LS phase.

This paper describes the ways in which the major rock-forming primary minerals (olivine, pyroxenes, amphiboles, feldspars, micas and chlorites) break down during weathering, the products that develop during this breakdown and the rates at which this breakdown occurs. The perspective chosen to illustrate this vast topic is that of the residual soil weathering profile. Different physical and chemical conditions characterize the various parts of such a profile. Thus, in the slightly weathered rock at the base of the profile, mineral weathering will take place in microfissures and narrow solution channels and the capillary water in such spatially restricted volumes may be expected to be close to equilibrium with the primary mineral. In these circumstances, the weathering product formed may be closely related to the primary mineral both compositionally and structurally. The saprolite higher up in the weathering profile may or may not retain the fabric and structure of the original parent rock, but in either case the close relationship observed between primary mineral and weathering product in the slightly weathered rock may be lost. This part of the profile will usually be affected by freely flowing drainage waters, the composition of which will be far from equilibrium with specific primary minerals. Weathering products which do form are likely to reflect the interaction between bulk water and bulk parent material. In the soil profile, the situation will be further complicated by organic ligands derived from decomposing organic matter or from the direct activities of soil microbes or plant roots. Thus, biological weathering will assume a much greater significance in this part of the profile compared with the mainly inorganic processes dominating in the saprolite and the slightly weathered rock. The general nature of any particular weathering profile will reflect the interactions between climate, topography, parent material, soil biota and time and superimposed upon this complexity, when considering how individual primary minerals break down in detail, will be factors related to the nature of the mineral itself. Particularly important in this respect is the inherent susceptibility of the mineral to weathering, which is related to overall chemical composition and structure, as well as the distribution and density of defects, dislocations and exsolution features, which often control the progress of the weathering reaction.

Kaolinite and synthetic γ-Al(OH)3 (gibbsite or hydrargillite) were reacted with phenylphosphonic, phenylphosphinic and 2-nitrophenol-4-arsonic acids. The products were studied by powder X-ray diffraction, transmission electron microscopy/selected area electron diffraction/ energy dispersive X-ray/Fourier transform infrared and simultaneous thermogravimetric/differential thermal analysis. The acids were not intercalated but, instead, easily destroyed the structure of the minerals. Lamellar Al phenylphosphonate and aluminium phenylphosphinate and phenylarsonate with polymeric linear-chain structures were formed from kaolinite. The reaction between gibbsite and the same acids yielded almost identical products. No evidence of formation of grafted kaolinite derivatives after the reaction with phenylphosphonic acid was found.

The purpose of this study was to investigate the impact of redox-induced changes in the organization of the clay fraction of a bulk vertisol using transmission electron microscopy. Chemical and X-ray powder diffraction (XRD) analyses indicated that the oxidized clay was composed of 32% kaolinite and 68% non-pure smectitic material, mostly a dioctahedral beidellite with octahedral Fe, according to Quantarg2 and DecompXR models.

The cation exchange capacity of the soil increased from 26.1 to 65 cmolc+ kg-1 due to structural iron (FeStr) reduction and dissolution of oxide coatings. Transmission electron micrographs revealed dramatic changes upon reduction. Oxides were dissolved and the smectite increased in particle darkness, lateral extension, thickness, compactness and stacking order. These changes were interpreted to be a consequence of sorption of ferrous Fe and reduction of FeStr, as found in previous studies on pure Fe-bearing smectites.

The alteration and transformation behaviour of montmorillonite (Wyoming bentonite) was studied experimentally to simulate the mineralogical and chemical reaction of clays in contact with steel in a nuclear waste repository. Batch experiments were conducted at 80 and 300ºC, in low-salinity solutions (NaCl, CaCl2) and in the presence or otherwise of magnetite and hematite, over a period of 9 months. The mineralogical and chemical evolution of the clays was studied by XRD, SEM, transmission Mössbauer spectroscopy and EDS-TEM. Experimental solutions were characterized by ICP-AES and ICP-MS. The main results are that no significant change in the crystal chemistry of the montmorillonite occurred at 80ºC, while at 300ºC, the presence of Fe oxides leads to a partial replacement of montmorillonite by high-charge trioctahedral Fe2+-rich smectite (saponite-like) together with the formation of feldspars, quartz and zeolites.

Image analyses, carried out on thin sections made in consolidated and sheared kaolinite test pieces, allow the identification of three ‘microstructural domains’: (1) the initial isotropic matrix; (2) a partly anisotropic matrix resulting from simple particle arrangement; and (3) an anisotropic matrix resulting from rearrangement plus flattening and delamination of particles.

In order to explain the micromechanisms of the clay matrix behaviour, this paper proposes to link the ‘microstructural domains’ represented in the e vs. log p Cam-clay diagram and domains of hydraulic conductivity in the k vs. e diagram.

The hydraulic conductivities are calculated following the Kozeny-Carman relations, which take into account the micro-arrangement of particles via a tortuosity calculation. The generation of 2D images shows that the preservation of the isotropic arrangement of particles is limited by a minimum porosity value. A decrease of the porosity value below this limit can be explained only by a progressive anisotropic rearrangement of the particles.

The microtexture behaviour, induced by the superimposition of the compaction, orientation and particle flattening and delamination stages, causes an anisotropy of the hydraulic conductivity which affects (1) the interstitial water flow direction, (2) the rotation of particles itself, and (3) the damage mechanism of the clay.

The hydrothermal reaction of kaolinite in the systems Li2O–K2O–MgO–Al2O3–SiO2–H2O–HCl and Li2O–Na2O–MgO–Al2O3–SiO2–H2O–HCl, at pH between 9 and 11, has been investigated at 200–250°C from 1 to 180 days.The X-ray diffraction study of the K-bearing system indicates that the solid products formed were Li-A(BW) zeolite, crystalline silica, and randomly ordered chlorite-smectite mixed layers, dioctahedral on average, with a chlorite:smectite ratio of ~1:4.Study by electron microscopy reveals, however, the presence of mixtures of very thin particles of smectite, di,trioctahedral chlorite and mixed-layer phases.The X-ray study of the solid products formed in the Na-bearing system reveals that the neo-formed phases were Li-A(BW) zeolite, analcime and partially ordered chlorite-vermiculite mixed-layers with high chlorite:vermiculite ratio. The transmission microscopic study of these phases shows the presence of dioctahedral ‘vermiculitic’ curved particles and di,trioctahedral chlorite-like particles.In both cases, long reaction times cause formation of a 7 Å phase with composition intermediate between kaolinite and serpentine.The composition of the solutions suggests that the stable phases would be chlorite/smectite mixed-layers, with compositions near tosudite in the case of the K-bearing reaction and both a dioctahedral phase (tosudite?) and a trioctahedral one (clinochlore) in the case of the Na-bearing reaction.

The mineralogy and geochemistry of the clay fraction of Victoria Land Basin (Ross Sea, Antarctica) sediments was investigated, to determine the origin of clay minerals and the features of authigenic smectite. The investigated core (CRP-3) is ~800 m long, mostly of Oligocene age. The clay fraction of the upper sequence consists of mica, chlorite and detrital smectite, while that of the central and lower part is largely made up of authigenic smectite. Authigenic smectites are ditrioctahedral, with a composition close to saponite, while detrital smectites such as Al-Fe beidellites are dioctahedral. Authigenic smectites have no illite mixed layers, show a higher degree of crystallization, higher MgO, Fe2O3, V, Cr, Co, Ni and Sc contents and lower SiO2, Al2O3, K2O, TiO2, Ba, Rb and Zr contents with respect to detrital clay minerals, and a clear depletion of LREE with respect to HREE. Authigenic smectite formed from the alteration of volcanic materials and clay minerals.

The excavation of a tunnel through a mudstone formation provides an opportunity to examine the effects of the modification of the physical and chemical environment on the rock. The mineralogical and chemical consequences of hydration-dehydration cycles and of oxidation have been evaluated in the case of the Toarcian mudstone formation at the Tournemire experimental site (France). Studies by X-ray diffraction and tansmission electron microscopy of both altered and preserved samples show that the introduction of air and condensed water causes the oxidation of pyrite and the subsequent generation of acid and sulphate-rich waters at the micron scale, in the local environment of pyrites. The fluid-clay particle interactions around the oxidized pyrites induce: (1) a statistical enrichment in Si of the I-S clay minerals; (2) an increase in the Fe(III)/Fe total ratio in some of the I-S particles; and (3) the dissolution of illite layers in mixed-layer I-S. These evolutions are consistent with the results of numerical modelling which reproduced the interaction between the clay particles and the acid water.

The adsorption and desorption of Hg(II) by humic acid (HA) previously adsorbed on kaolin was studied. In the range of HA concentration investigated (0.0 –26.9 mg g–1), the Hg(II) adsorption capacity of kaolin at pH 4 is enhanced by the presence of HA. For the complexes with the highest HA concentration and for low Hg(II) initial concentrations, adsorption was lower, i.e. as HA concentration on the complexes increases, Hg(II) equilibrium concentration also increases. This behaviour is due to the increasing presence of dissolved organic matter as the HA concentration on the complexes increases. The dissolved organic matter is able to form a soluble complex with Hg, thus decreasing adsorption. Hg(II) adsorption from a 2.5×10–5 MHg(II) solution was influenced by pH. For kaolin, a pHmax (pH where maximum adsorption occurs) of 4.5 was observed. At pH values >pHmax retention decreased with increasing pH. This same behaviour was observed for the kaolin- HA complex containing the lowest HA concentration (6.6 mg g –1). For the other kaolin-HA complexes there was little effect of pH on Hg(II) adsorption between pH 2.5 and pH 6.5. The presence of HA increased the adsorption of Hg(II) on kaolin all along the pH range studied. Desorption experiments showed that the amount of Hg(II) desorbed was quite low (<1%) for all the HA and Hg(II) concentration range studied, except for the kaolin at acid pH (pH 2.5) where the Hg(II) released was >50% of Hg(II) previously adsorbed. The presence of HA dramatically reduced this percentage of desorption to values of <3%, indicating reduced risk of toxicity problems in surface and subsurface waters. The addition of Cu(II) did not favour any Hg(II) desorption, even though Cu exhibits a strong affinity for organic matter.

Lateritic weathering profiles developed on serpentinized peridotites of Murrin Murrin (Western Australia) exhibit thick smectite zones (10–15 m). The smectites from plasma and fissures were characterized by XRD, chemical analyses (ICP-AES, SEM-EDX and TEM-EDX) and Mo¨ssbauer spectroscopy. These Fe-rich smectites, previously described as nontronites, are in fact more complex. Their layer charges originate from both the tetrahedral and octahedral sheets. Plasma and notably fissure smectites exhibit, from the bulk sample scale to the particle scale, large and continuous Al for (Fe+Cr) substitutions, covering a chemical gap previously described for dioctahedral smectites ranging between nontronite and beidellite end-members. Lastly, they exhibit an octahedral occupancy slightly above 2, due to a low (Mg+Ni) trioctahedral contribution. Thus, the smectites occurring in weathering profiles of ultrabasic rocks can have actual chemistries intermediate between four dioctahedral end-members (beidellite, nontronite, montmorillonite and previously rarely described ferric-montmorillonite) and a trioctahedral one ((Mg+Ni)-saponite).

Initial stages of the gel-to-kaolinite transformation were studied using HRTEM. Spherical aggregates of kaolinite crystals were produced during the synthesis of kaolinite by hydrothermal treatment of Si-Al amorphous gels. Prior to sphere formation, gels transform into pseudospherical domains that have a Si/Al ratio of one and display no SAED pattern. The spherical particles consist of radially arranged sectors of stacks of planar crystallites. Crystals display nonbasal spacings of 4.5, 4.2 and 3.8 Å and a basal spacing of 7.1 Å , the c* axis following the radius of the sphere.

Interpretation of the 3D nanostructure of the spheres is difficult. The c* axis exhibits a radial disposition, but the relative orientation of the a* and b* axes in neighbouring crystallites may produce bent layers or incoherent contacts. In addition, curved layers with a d spacing of 7.4 Å may be attributed to halloysite layers collapsed under microscopy conditions. The disappearance of the spheres during the hydrothermal treatment is probably due to preferential dissolution of either highstress areas near bent layers or non-crystalline material filling crystal boundaries. Dissolution leads to sphere disaggregation and allows the component columnar crystals to continue to grow. Observations of the gel matrix suggest that under our experimental conditions kaolinite crystallizes via an in situ transformation of the gel.

K-Ar isotopic dating of very low-grade metamorphism affecting Triassic-Jurassic rocks in the Coastal Range of central Chile was carried out on whole rocks and their <2 mm size fractions. In the study area, a regional-burial low-grade metamorphism at anchizone conditions (T ≤190°C) and low-pressure conditions (P ≥1.3 kbar) has been described. The highest observed temperatures are related to a contact metamorphism produced by nearby Jurassic intrusions, with a P-T estimate at the immediate contact zone of ~650–690°C and 4 kbar.

The whole-rock K-Ar age of 174±5 Ma is interpreted as belonging to the contact metamorphism due to the intrusion of Jurassic plutons (165±5 Ma to 175±5 Ma). A time-interval of ~20 Ma between the diagenesis (206 Ma) and the anchizonal very low-grade metamorphism (181–184 Ma) is obtained, and a rate of subsidence of ~120 m/Ma is proposed for these Triassic-Jurassic basins. A thermal influence on the burial, very low-grade, regional metamorphism is invoked.

A natrolite-cemented palagonite ash tuff unit is reported in a palaeo-basin in northeast Jordan. Phillipsite and chabazite are also identified. The zeolites were formed due to transformation of volcanic glass granules into palagonite by the reaction with percolating water in a closed hydrological system. Consequently, Si, Al, Ca, Na and K are leached out and precipitated in a series of authigenic layers developed at the extreme edge of the granules. The recorded paragenetic sequence is smectite → phillipsite → chabazite → natrolite → analcime → calcite. The natrolite studied is chemically similar to those reported in the literature with minor variations. The phillipsite and chabazite studied are chemically different from the other Jordanian phillipsite and chabazite reported. The latter are chemically equivalent to those formed under open hydrological systems, whereas the phillipsite and chabazite in this study are chemically equivalent to those formed in saline lakes and arid soil environments. This conclusion is based on the (Na+K)/(Na+K+Ca+Mg) ratio and the Si/Al ratio.

The influence of grinding on colour and particle-size properties of talc and smectite from a white bentonite were studied and compared with a fine-grained calcite from a chalk. Grinding decreased the grain size of all three minerals. The crystallite size and structure of smectite was not affected but the crystallite size of talc decreased. The Si–O–Mg and Mg–O bonds of talc were disrupted and cation exchange capacity increased with increasing grinding. Delamination of talc crystallites was observed in the initial stages of grinding, whereas with more intense treatment, amorphous material was formed. Comminution improved the colour properties of all three minerals, namely brightness, L* (lightness) and ΔE*ab (deviation from perfect white diffuser). Grinding time exerts greater influence on the reflectance from calcite surfaces than from clay minerals. This difference is attributed to continuous formation of progressively smaller diffuse reflection units forming a smoother calcite surface. Decrease of grain size does not form considerably smaller diffuse reflection units in clay minerals unless delamination takes place. With prolonged grinding, amorphization forms additional diffuse reflection units and a smoother surface due to comminution.

Mineralogical and chemical variations were studied in the upper half of a 1 m thick discontinuous bentonite bed interlaminated in the Lower Cenomanian sedimentary formations of the northern Aquitaine basin (France). X-ray diffraction patterns obtained from the <2 mm fraction in the Ca and K-saturated states were decomposed and compared to those calculated from decomposition parameters. They revealed the presence of two highly expandable illite-expandable (I-Exp) mixedlayer minerals (MLMs). The relative proportions of the two MLMs evolve steadily with depth leading to the decrease of the cation exchange capacity and of the (Na + Ca) content towards the centre of the bentonite bed. However, the system is essentially isochemical and Mg, Al, Si, K and Fe are roughly constant in the bulk samples. It is thought that the mineralogical zonation results from the initial stages of the smectite formation in an ash layer.

In the Ca-saturated state, the expandable component of these MLMs was for the most part homogeneous with the presence of 2 sheets of ethylene glycol molecules in the interlayer. However, the heterogeneous hydration behaviour of these expandable layers was enhanced by the K-saturation test. From this test, the presence of three layer types with contrasting layer charge was evidenced from their contrasting swelling abilities. The C12-alkylammonium saturation test applied to samples in which the octahedral charge had previously been neutralized (Hofmann-Klemen treatment) showed that the tetrahedral charge is located on specific layers. These layers are responsible for the heterogeneous hydration behaviour. Low-charge smectite layers are mostly octahedrally substituted, whereas for intermediate- and high-charge layers this montmorillonitic charge is complemented by additional tetrahedral substitutions (0.30 and 0.35–0.40 charge per O10(OH)2, respectively).

2-line ferrihydrite stored in water at ambient temperatures from 4 to 25°C and at ten different pH values between 2.5 and 12 for up to 10–12 y transformed to both goethite and hematite at all temperatures and pH values except at pH 12 where only goethite was formed. The rate and degree of transformation (20–100%) increased with increasing pH and temperature. The hematite/ (hematite+goethite) ratio varied between 0 and ~0.8, increased with increasing temperature and showed a strong maximum at pH 7–8 which increased from 0.1–0.2 at 4°C to 0.7–0.8 at 25°C. The maximum coincides with the zero point of charge of ferrihydrite where its solubility and, thus, its via-solution transformation rate to goethite are minimal. We assume, therefore, that in this pH-range the (slower) via-solution transformation to hematite can more efficiently compete with that to goethite.

Two sedimentary profiles, at 18 km and at 125 km from the Rhône River mouth were selected to study the steps of glauconitization inside green (glaucony) grains, in a temperate marine environment. The proximal site is characterized by a greater content of alpine minerals (chlorite, illite) than the distal one. In the proximal site, pellets at a younger level demonstrate a largely inherited mineral composition. In the older level, representing the most advanced stage of glauconitization, there is a mixed-layer glauconite-nontronite (G-N) phase with 20% glauconite-80% nontronite in dark green grains. In the distal site, more evolved glaucony has up to 92% glauconite in the G-N. In spite of this difference, the glauconitization process developed similarly in the two sites. The relatively low Fe content in the mud-matrix does not reflect the concentration of this element inside the grains. During diagenesis, most of the inherited minerals disappear, making way for neoformed mixed-layer glauconite-nontronite.