High-quality kaolins are produced from two sites in the Capim River area in Pará State, northern Brazil. One mine is operated by Rio Capim Caulim (RCC) owned by Imerys and the other by Pará Pigmentos S.A. (PPSA) owned by Caemi (CVRD Group). The kaolin deposits are located on low-relief plateaux with a lateritic cap. The kaolin strata are in the Ipixuna Formation of Upper Cretaceous Age. There are two distinct kaolin layers, a 4–5 m thick soft kaolin which is overlain in the southern portion of the basin by a 4–5 m thick hard kaolin. The soft and hard designations refer to particle size, with the soft kaolin being relatively coarse and the hard kaolin very fine. The kaolin is mined, partially beneficiated, and pumped through pipelines to the port at Barcarena on the Guama River, a large tributary of the Amazon River. The PPSA kaolin is fully processed at the plant near the mine site and pumped to Barcarena where it is spray dried. The RCC kaolin is only partially processed at the mine site. This partially processed kaolin is pumped to Barcarena where it is beneficiated. The finished kaolin is high quality and is shipped to North and South American, European, and Asian paper-coating markets. More than 1.6M tons were shipped from Barcarena in 2005.

Kaolinite aggregates are the major alteration product in the strongly deformed areas of a shear zone developed in contact-metamorphosed slates from the Southern Iberian Massif near Jaén (SE Spain). Muscovite and Fe-rich chlorite in strain shadows of broken andalusite crystals were observed in slates from less deformed areas. The presence of phyllosilicate packets nearly perpendicular to each other and veinlets parallel to {110} of andalusite reveal the importance of cleavage-controlled fracturing of andalusite to the mineral reactions. The compositional similarity between kaolinite and andalusite suggests a direct transformation of andalusite to kaolinite in the strongly altered area. The absence of clear preferred orientation of phyllosilicates relative to andalusite, and the compositional differences of andalusite with muscovite and chlorite from the less altered samples, indicate andalusite dissolution and chlorite-muscovite precipitation during a first mineral-growth stage. Muscovite-kaolinite and chlorite-kaolinite intergrowths indicate a later retrograde replacement stage.

Soil clay minerals in recent natural polders react on a human timescale in response to local environmental conditions. With increasing age, the mineral reaction leads to the dissolution of the chlorite component and a composition change of the different illite-smectite mixed-layer minerals (I-S MLMs): i.e. smectite layer content decreases and illite content increases. The process of oxidation, which is proven by magnetic susceptibility to trigger clay mineral reaction, changes the mineralogical composition of the sediment above the redox front. The mineral changes appear to be a non-linear function of time. In natural conditions the process lasts >1000 y. However, anthropoic forcing such as artificial drainage accelerates the oxidation reaction to complete the whole process in a few tens of years.

Rock weathering has been investigated from atomic to global scales through the different but complementary approaches of mineralogy, petrography, geomorphology and geochemistry. The sequences of mineral reactions involved in the alteration process are now well known. They explain the global trend of weathering phenomena but do not account for the actual rock transformation dynamics. In particular, they ignore the intimate relation of the mineral reaction progress with the increase in connected porosity. At the hand specimen scale, heterogeneity is the rule: mineral reactions are controlled by local physicochemical conditions. Alteration processes depend largely on the rock microstructure properties. They proceed through nearly-closed, semi- and completely open microsystems which are interconnected by fractures or pores. Before being leached out by the solutions which flow in the large fractures (flux), the soluble elements migrate inside the connected porosity through chemical diffusion. The dissolution of the primary minerals is mediated through local gradients of chemical potential. With increasing alteration, the rock porosity increases, as does the length of the fluid passageways and their constrictivity and tortuosity. Consequently, the apparent diffusion coefficient for the most soluble elements decreases. The amplitude of the chemical potential gradients for the most soluble elements is reduced by the progressive coating of the reactive surfaces by clays and Fe oxyhydroxides. The residence time of these elements inside the weathered rock increases as alteration progresses; an effect enhanced by their temporary adsorption on the exchangeable sites of clays and Fe oxyhydroxides. Consequently, the weathering rate decreases with time. A possible new way to calculate weathering rates could be to measure the residence time of soluble elements inside the different microsystems during their migration towards the diluted solution which occurs in the large fractures.

Fe-rich dioctahedral smectites are the main constituent of clays in Çamlıca Region of Turkey. The structural, chemical and morphological characteristics of these smectites after washing are examined by X-ray diffraction, electron microscopy, inductively coupled plasma mass spectrometry and Fourier transform infrared spectroscopy. Smectite particles occur as individual flakes 0.2–2.0 μm in size. These flakes are often aggregated into clusters up to 6.0 μm in size.

Magnetite is a redox active Fe oxide common in most soil and sedimentary environments. In this study, we investigated magnetite transformations under extreme alkaline conditions (0.1–2 mol l–1 NaOH) similar to those found under high-level radioactive waste storage tanks at the Hanford site in the State of Washington, USA. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that magnetite was transformed into maghemite and goethite, and the XRD peak intensities for goethite increased with NaOH concentration. Goethite was presumably formed through reconstructive dissolution/crystallization reactions that can be written as: Fe3O4 + OH– + H2O = γ-Fe2O3 + Fe(OH)3–; 2Fe(OH)3– + 1/2O2 + 2H+ = 2α-FeOOH + 3H2O. Some of the newly formed maghemite may also redissolve to form goethite at greater NaOH concentrations.

High-resolution synchrotron X-ray diffraction recorded on a collection of palygorskites with different chemical compositions (obtained by analytical electron microscopy) permits unambiguous correlation of the crystallographic parameters a (or a sin β if a monoclinic phase is considered) with the nature of the octahedral sheet, i.e. with both the number of octahedral positions that are occupied and the type of octahedral cation. No significant changes in the lattice parameters b and c are observed. The unit cell modification consists essentially of an expansion in a as the number of cations with larger ionic radii (Mg2+ and Fe3+) predominates over smaller cations (Al3+). A linear dependency of a (or a sin β) on the chemical composition of the octahedral sheet was obtained that can be used for classifying palygorskite into compositional groups, using only conventional diffraction data, without the need for chemical analyses.

Twenty nine Fe oxide concentrates of Thai soils formed on basalt, sandstone, shale/limestone and granite were investigated. Goethite and hematite are relatively more abundant in granitic and basaltic soils, respectively. Values of Feo/Fed range from 0.01 to 0.28 indicating that free Fe oxides are mostly crystalline.

There are no systematic differences in unit-cell dimensions for goethite and hematite in soils on different parent materials. Mean crystallite dimensions calculated from the 110 reflections are greater for hematite than for goethite. Aluminium substitution varies from 8 to 24 mole% for goethite and from 4 to 17 mole% for hematite. The dehydroxylation temperature for goethite ranges from 285ºC to 320ºC. The goethite in basaltic soils has a smaller crystal size and Al substitution, as well as a lower dehydroxylation temperature, compared to soils on other parent materials. The dehydroxylation temperature of goethite is positively related to Al substitution (R = +0.58), MCD110 (R = +0.49) and Ald (R = +0.53). The Mn, Ni, Cr, V and P in these soils occur in Fe oxides rather than as discrete minerals.

Alternative Fenton and Fenton-like systems based on natural Fe oxides are described. The collected materials were modified through controlled reduction with H2 and were characterized by chemical analysis, X-ray diffraction, saturation magnetization measurements, and Mössbauer spectroscopy at 298 and 110 K. The catalytic activities of these original and modified materials were tested by studying the decomposition of H2O2 and the discolouration of methylene blue. Iron oxides present in the samples were mainly hematite and subordinate goethite which, after controlled reduction, were converted to metallic iron and magnetite. The mixture of Fe0 and magnetite in one of these materials was significantly more efficient at H2O2 decomposition and the discolouration of methylene blue than the original Fe3+ oxides. These results suggest that Fe2+ is essential to produce an active Fenton system.

Iron cations in the octahedral sheet are a disadvantage to the industrial application of palygorskite clays. In this study, a palygorskite sample from eastern China (Mayaoshan deposit, Jiangsu Province) is shown to have an Fe content that is much greater than usual. The structural formula of the Fe-rich palygorskite sample was established as (Si7.48Al0.52) (Al1.24Fe0.94Mg1.77Ti0.03⁏1.02)O20(OH)2(OH2)4. The palygorskite is seen to be dioctahedral according to the structural formula, consistent with Fourier transform infrared data. Occurrences of AlFe3+ɏOH and Fe3+Fe3+ɏOH vibrations in the OH-stretching and -bending regions show that Fe atoms occupy inner sites of octahedral sheets. A Mössbauer spectrum confirmed that Fe ions occupy inner octahedral sites as trivalent Fe cations (Fe3+).

A scanning and transmission electron microscopy study has been performed on Oligocene glacio-marine sediments, Devonian sandstones, and Jurassic dolerites recovered during CRP-3 drilling in the Ross Sea (Antarctica). Newly formed clay minerals occur in the rock matrices and as fillings in veins and faults which crosscut the whole sequence. Authigenic clays in sediments consist of beidellite-montmorillonite, berthierine/chlorite intergrowths and illite. Al,K-rich smectites and kaolinite occur in the Devonian sandstones. Saponite, berthierine/chlorite intergrowths, and Fe-hydroxides develop in the altered dolerites. Hence, the composition of the secondary phases depends also on the geochemistry of the rock they grow in. Within each sample, the same authigenic minerals form in the matrix and in the vein/fault. Clays precipitated from fluids, with variable fO2 values, which circulated in the system during the contemporaneous diagenetic and faulting events.

Given that reservoirs contain most of the leached materials from soils, we have studied the sediments accumulated in the bottom of two groups of reservoirs developed under different climatic conditions and thus with contrasting rates of weathering/erosion regimes. Through detailed comparative study of clay minerals of the parent rocks and soils with the clay fractions of the dam sediments, we have concluded that, during cycles of erosion-transport-deposition, the leached materials have complex transformation mechanisms, making them much more active in the environment. All clay-mineral groups are well represented in the reservoir sediments, including abundant mixed-layer and partly disordered minerals. Moreover, the sediments are nutrient-rich and potentially useful as agricultural fertilizers and hence in reversing the declining soil productivity in some regions.

Green rusts, GRs, can act as both sorbents and reductants towards selected pollutants. Organo-GRs are expected to combine these properties with a high affinity for hydrophobic substances. A novel organo-GR, GRLAS, was synthesized by incorporating a mixture of linear alkylbenzenesulphonates (LAS) into the interlayer space of synthetic sulphate green rust, GRSO4 . Mössbauer analysis of GRLAS indicates that the structure of the organo-GR is very similar to that of the initial GRSO4 with regard to the FeII/FeIII ratio and local coordination of Fe atoms. X-ray diffraction demonstrates that the GRLAS formed was well ordered, although a mixture of surfactant was used for intercalation. The basal spacings of the GRLAS and the kinetics of the ion-exchange process were dependent on the initial surfactant loading; basal spacings of ~2.85 nm were obtained at LAS solution concentrations >10 mM. The ratio LASadsorbed/SO42–desorbed significantly exceeded the stoichiometric ratio of 2 during the initial part of the ion-exchange process (t = 5 h). However, this ratio was reached progressively with time. GRSO4 preferentially sorbed LAS homologues with long alkyl chains over short ones. Carbon tetrachloride was successfully adsorbed into GRLAS. The adsorption isotherm was linear with a distribution coefficient, Kd, of 505±19 litre kg–1.

Rectorite (REC) was modified with dodecyl benzyl dimethyl ammonium chloride (1227) to form an organic-modified rectorite, termed OREC. The OREC was used as a filler additive to modify gel polymer electrolytes (GPEs) which consisted of polymethyl methacrylate (PMMA), propylene carbonate (PC) and LiClO4. Studies of ionic conductivity and viscosity of liquid electrolytes and pure PC, respectively, clearly showed that these properties are greatly influenced by temperature and the amount of OREC added; a consequence of the interactions between the components of CPEs. The Fourier transform infrared (FTIR) spectroscopy results indicated that there were two kinds of interaction: namely (1) a strong hydrogen bond between Si–OH and C=O of PC and (2) a weak interaction between Li+ and C=O. Inverse gas chromatography (IGC) research supported the FTIR interpretation, indicating that the two interactions exist and that the H bond is the stronger of the two. In CPEs, the polymer matrix of PMMA merely supports the active components and does not influence the interactions between them. The OREC greatly increased the crucial plasticizer maintenance property when the amount of clay added was optimum.

The mineralogical characteristics of authigenic palygorskite occurring with chlorite and illite in Miocene sediments in Linxia basin were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). The XRD results suggest that the mineral composition of the sediments includes mainly quartz, chlorite, illite, calcite, plagioclase, orthoclase, minor palygorskite and small amounts of gypsum and ankerite. Two kinds of palygorskite were observed in the sediments, relatively straight fibrous particles found in matted, felted masses associated with platy chlorite and silky aggregates found in the void spaces. The former probably replaces chlorite grains, growing from the edges or the fissures of chlorite particles. Chlorite grains exhibit bay-shaped or rounded edges, with ambiguous felted boundaries between chlorite particles, indicative of an intensive dissolution process and the growth of palygorskite at the expense of chlorite. Palygorskite is also observed as inclusions within calcite, sprouting from or coating calcite surfaces, suggesting that palygorskite crystallized from solution. The textural relations of palygorskite and the occurrence of ankerite and the characteristically Fe-bearing palygorskite in the sediments suggest the destruction and hydrolysis of chlorite. The ankerite seems to be preferentially present in the void spaces, closely associated with chlorite and illite; fibrous palygorskite crystallizes at the edges of these clay mineral particles and the platy clay mineral particles are gradually replaced by fibrous palygorskite crystals, suggesting that alteration of chlorite to palygorskite involves an interaction with water during the diagenetic process.

Kaolinite-smectite mixed-layers have been found to have a complex structure with smectite and kaolinite domains within layers. Here we further investigate this structure in samples with 0–80% kaolinite layers, as determined by X-ray diffraction, by means of magic angle spinning nuclear magnetic resonance (MAS NMR) of 29Si and 6Li. The 29Si NMR experiments were carried out on two samples (55 and 80% kaolinite layers), before and after their exchange with Mn2+, a paramagnetic ion that causes NMR signal loss from neighbouring nuclei, in order to investigate the distance between Mn ions and Si atoms in kaolinite sites. The 29Si NMR intensity from such sites (at ~–91 ppm) was reduced upon Mn exchange, indicating that some Mn ions are located near kaolinite Si sites. The position of the 6Li peak changes slightly (–1.3 to –1.8 ppm) but progressively with increasing kaolinite content (0–80% kaolinite layers) of four K-S specimens, suggesting two slightly different chemical environments for interlayer Li, one related to smectite and the other to kaolinite. The two sets of experiments are consistent with a complex structure of kaolinite-smectite, including smectite and kaolinite domains within layers and/or interlayers of varying smectitic and kaolinitic character.

Ferric illite in the Neoproterozoic Penganga Group, southern India, occurs in a lenticular unit of reworked arkoses conformably enclosed in carbonate mudstones, deposited in a shelf-margin carbonate slope setting influenced by deep marine sediment gravity flows. The structures and textures of the arkoses suggest emplacement by fine-grained debris flows and deposition in channels incised into the carbonate slope.

Ferric illite is sparse in the arkoses and has small concentrations and grainsizes within the same size fraction of the associated detritus, uniform chemical composition and an association with reworked facies. It consists predominantly of granular grains that are mostly sorted spherical, ovoid, capsule-shaped and vermicular peloids; many broken and micaceous. These attributes provide a comprehensive framework for suggesting an allogenic origin for the ferric illite previously interpreted as authigenic. The methodology adopted here is a useful approach in the interpretation of in situ vs. reworked origins of glauconitic minerals.

A mineralogical and microtextural study of Somosaguas Miocene deposits, located in the Madrid Basin (western Madrid, Spain), was carried out using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and optical microscopy, whereas crystal chemistry data were obtained by analytical electron microscopy-transmission electron microscopy and electron icroprobe analysis. Four stratigraphic sections were studied, compising detrital rocks representing intermediate and distal facies from alluvial fan deposits. The predominant source area of these sediments was the granitic rocks of the Spanish Central System with a lesser contribution of metamorphic rocks. Clayey arkoses are the most abundant rocks of these sections, typical of granite alteration under warm, semi-arid climates. The mineralogy is characterized by phyllosilicates, followed by feldspars and quartz. The data obtained reveal mineral mixtures of detrital (quartz, feldspars, kaolinite, micas and chlorite), transformed (illite and beidellite) and neoformed (montmorillonite) origin. Clay minerals resulted from interactions between detrital minerals and meteoric waters. Two trends of degradation of micas are detected. The first shows a transition from muscovites and dioctahedral illites, to beidellites. The other trend is defined by the biotite degradation to beidellites with different layer charge and octahedral Fe content. Montmorillonites were neoformed from the hydrolysis and weathering of primary minerals (feldspars and muscovite). Magnesian clay minerals such as sepiolite, palygorskite and trioctahedral smectites, extremely abundant in the centre of the basin, were not detected in Somosaguas sediments.

The rheological and filtration properties of a Tunisian clay are presented and compared with those of Wyoming bentonite. The study was part of an evauation of Tunisian mining resources in general, and of the bentonitic deposits in particular. Qualitatively, the two clays exhibit the same rheological and filtration behaviour but quantitatively the properties of purified Wyoming bentonite are distinctly better at the same concentration. The difference can be related to the mineralogical structure and the presence of 13% illite in the Tunisian clay. Standard tests show that the rheological behaviour of the purified Tunisian clay is close to that of the raw Wyoming bentonite and conform to the American Petroluem Institute (A.P.I.) standards for medium-depth drilling formulations.

In liquid-filled batteries, the liquid electrolytes may escape or present a fire hazard and an inert spacer is needed to separate the electrodes. Alternative polymer-based electrolytes are of current technological interest. Solid polymer electrolytes are non-volatile, non-corrosive materials, which can readily be processed into any shape or size. However, despite possessing the required mechanical properties, they have inherently lower conductivity. Gel-based systems are an attempt to strike a balance between the high conductivity of organic liquid electrolytes and the dimensional stability of a solid polymer.

Rectorite was modified with dodecyl benzyl dimethyl ammonium chloride to form organic-modified rectorite (OREC). OREC was used as a filler additive to modify gel polymer electrolytes (GPEs) and prepare composite gel polymer electrolytes (CPEs) which consisted of polymethyl methacrylate (PMMA) used as a polymer matrix, propylene carbonate (PC), used as a plasticizer, and LiClO4, used as a lithium ion producer. A variety of physical and chemical techniques was used to characterize the CPEs. The interlayer d spacing of OREC was much larger than that of the initial rectorite (2.22 nm). OREC also possesses a fine microscopic structure, and has a hydrophobic surface. Molau and XRD analysis of CPEs indicate that OREC has good compatibility with the components of CPEs and can be dispersed well. The effects of temperature and OREC dose on properties were studied. The temperature dependence of ionic conductivity of CPEs is well fitted by the VTF (Vogel-Tamman-Fulcher) relation. OREC doses of 5 phr gave the greatest ionic conductivity. This amount also greatly increased the plasticizer maintenance levels. Due to the occupancy of free volume space in the polymer matrix of CPEs by OREC, the bulk resistance of the CPEs was lowered and the glass transition temperature (Tg) increased. The sheet structure of OREC is thought to improve the decomposition temperature of CPEs.