The level of Fe impurities in 2 well-crystallized kaolinites was modified (by addition or chemical removal treatment) to analyze the Fe influence in the aluminosilicate zeolite synthesis.

The original and modified clays were heat-treated in order to change their reactivity for zeolite A synthesis, and their thermal transformations were studied by X-ray diffraction (XRD), determination of point of zero charge (PZC) and infrared (IR) techniques. It was established that many structural changes took place, regardless of the Fe clay content. Furthermore, the presence of Fe species in alkaline solution or in the solid phase did not seem to greatly influence the zeolite crystallization, because only small differences in the conversion values among samples with different Fe contents were registered. The crystallization process seemed to be related mainly to AI coordination changes produced by the thermal and Fe removal treatments used.

Microbial reduction of clay mineral structural Fe(III) decreases the swelling of nontronite gels, most importantly at intermediate oxidation states (40 to 80 cmol Fe(II) kg−1 clay). The purpose of this study was to establish whether microbial reduction of structural Fe(III) decreased the swelling of other Fe-bearing smectites and to discern the influence that organic compounds of microbial origin (bacterial cells, cell fragments and/or exudates) may have on clay swelling and texture. Structural Fe(III) was reduced by incubating smectite suspensions with either a combination of Pseudomonas bacteria or a mixture of anaerobic bacteria. The influence of organics on clay swelling was estimated on smectites suspended in either organic or inorganic media in the absence of bacteria. The gravimetric water content of the reduced clay gels equilibrated at various applied pressures was recorded as a function of Fe oxidation state. Transmission electron microscopy (TEM) was employed to determine the influence of bacteria and type of media on the texture of reduced smectite gels. Reduction of structural Fe(III) by bacteria decreased the swelling pressure of all Fe-bearing smectites. Increased clay swelling, due to the presence of organics (organic medium, exudates or cell fragments), was correlated to the total Fe content, the extent of structural Fe reduction, as well as the initial swelling characteristics of the Fe-bearing smectites. High structural Fe(II) contents (>50 cmol Fe(II) kg−1) resulted in increased attractive forces between clay platelets that decreased clay swelling, even in organic medium suspensions. Microbial reduction resulted in increased face-face association of individual clay layers, forming larger and more distinct crystallite subunits than in nonreduced clay gels. But, perhaps more importantly, microbial reduction of structural Fe(III) resulted in an increased association between crystallite subunits and, thus, an overall larger particle size and pore size distribution, due to the interaction of bacteria ceils, cell fragments and organic exudates.

Swelling clays may play a major role in the underground disposal of high-level nuclear waste (HLW) in deep geological formations. A multibarrier concept including a waste container, a steel overpack, an engineered barrier consisting of compacted clay (buffer) and the host rock is a potential technique for such HLW disposal. It is anticipated that H2 will be the main gas generated, mainly by anaerobic metal corrosion during disposal lifetime. After complete resaturation, the clay barrier will have a very low permeability and H2 may accumulate in the space between the overpack and the clay barrier. This could result in pressures exceeding the resistance of the clay and damage to the entire engineered barrier system (EBS).

The French Atomic Energy Commission (CEA) has performed an experimental program on H2 gas migration in a French clay referenced Fo-Ca. The tests were conducted with a specific odometer-type cell developed by the Power Reactor and Nuclear Fuel Corporation (PNC) in Japan. Permeability tests on compacted Fo-Ca clay samples of specific dry densities between 1.6 and 1.9 and for water saturation degrees between 70 and 100% provided significant H2 permeability data (ranging from 10−15 to 10−21 m2). Gas migration experiments were also performed to study the behavior of Fo-Ca clay under high gas pressure. Two kinds of gas transport threshold pressures were detected in unsaturated compacted clay. The first one, called “critical pressure”, is the pressure over which a gas outflow migrates into the clay. This pressure probably exceeds the capillary pressure of the largest pores within the clay. The second one, called “breakthrough pressure”, is detected with increasing gas injection pressure. A sudden rise of gas outflow is subsequently observed. The occurrence of the gas breakthrough is associated with the aperture and propagation of preferential gas transport pathways in the clay. This is apparently linked to the hydromechanical properties and stress state of the clay. When clay samples are not fully watersaturated, the critical pressure is always lower than the breakthrough pressure. However, when the clay is saturated, the 2 pressures appear to be very close. Finally, this study showed that breakthrough pressure—a key parameter for the long-term stability of the clay buffer—varies considerably with the gas injection increments and with the size of the sample. The results of these experiments are consistent with those reported previously by other investigators.

The microtextural changes in the kaolinization of primary phyllosilicates including biotite, sericite, clinochlore and muscovite were investigated by scanning electron microscopy (SEM) and microchemical analysis of thin sections of weathered anorthosite. Kaolinization began at grain edges and propagated toward the interior. Grains were highly fanned out from the edges and exfoliated into several flakes along the basal cleavages, producing lenticular voids. Finally, long vermicular kaolinite pseudomorphs were formed after primary phyllosilicates. Statistical analysis showed a ninefold increase in volume during the kaolinization of biotite, suggesting that most AI in the kaolinite was imported from ambient weathering solution. Weathering primary phyllosilicates supplied templates suitable for the thick epitactic overgrowth of kaolinite to form long vermicular pseudomorphs. AI was sufficiently available due to the intense weathering of soluble anorthosite. Although present in small amounts, primary phyllosilicates gave high volumetric and mineralogical contributions to the weathering profiles by facilitating kaolinite precipitation.

The transformation of smectite into kaolinite and kaolinite-smectite interstratification were studied in samples belonging to the Argiles Plastiques formation of the Paris basin, by high-resolution transmission electron microscopy (HRTEM). Two original smectite phases, 1) beidellite with 1-nm-thick layers, and 2) beidellite-montmorillonite with 1.25-nm-thick layers, are progressively transformed into kaolinite-smectite mixed-layer minerals, and into kaolinite. As the percentage of kaolinite layers increases in the interlayered minerals, the kaolinite-smectite layer sequences, initially disordered, become locally more ordered, with the presence of KS and KKS units repeated 2 to 4 times (K = kaolinite layer, S = smectite layer). Two solid-state mechanisms seem to be responsible for the formation of kaolinite: 1) the transformation of 1 smectite layer into 1 kaolinite layer, denoted S → K, by stripping of a tetrahedral sheet and the adjacent interlayer region; 2) the intercalation of 1 kaolinite layer into smectite, denoted 0 (zero)→K. Structural and chemical incidences of these mechanisms are discussed.

We measured the visible to near-infrared (IR) spectra of 176 synthetic and natural samples of Fe oxides, oxyhydroxides and an oxyhydroxysulfate (here collectively called “Fe oxides”), and of 56 soil samples ranging widely in goethite/hematite and goethite/lepidocrocite ratios. The positions of the second-derivative minima, corresponding to crystal-field bands, varied substantially within each group of the Fe oxide minerals. Because of overlapping band positions, goethite, maghemite and schwertmannite could not be discriminated. Using the positions of the 4T1←6A1, 4T2←6A1, (4E;4A1)←6A1 and the electron pair transition (4T1+4T1)←(6A1+6A1), at least 80% of the pure akaganeite, feroxyhite, ferrihydrite, hematite and lepidocrocite samples could be correctly classified by discriminant functions. In soils containing mixtures of Fe oxides, however, only hematite and magnetite could be unequivocally discriminated from other Fe oxides. The characteristic features of hematite are the lower wavelengths of the 4T1 transition (848–906 nm) and the higher wavelengths of the electron pair transition (521–565 nm) as compared to the other Fe oxides (909–1022 nm and 479–499 nm, resp.). Magnetite could be identified by a unique band at 1500 nm due to Fe(II) to Fe(III) intervalence charge transfer. As the bands of goethite and hematite are well separated, the goethite/hematite ratio of soils not containing other Fe oxides could be reasonably predicted from the amplitude of the second-derivative bands. The detection limit of these 2 minerals in soils was below 5 g kg−1, which is about 1 order of magnitude lower than the detection limit for routine X-ray diffraction (XRD) analysis. This low detection limit, and the little time and effort involved in the measurements, make second-derivative diffuse reflectance spectroscopy a practical means of routinely determining goethite and hematite contents in soils. The identification of other accessory Fe oxide minerals in soils is, however, very restricted.

Solid phase transformation and metal solubility were monitored after coprecipitation of Cd2+, Cu2+, Pb2+ and Zn2+ with Fe3+ to form ferrihydrite by titration to pH 6. The (co)precipitates were aged at room temperature for up to 200 d and subsequently heated for 60 d at 70 °C. The mode of (co)precipitate formation, rapid and slow titration, was also investigated. Metal solubility was measured by anodic stripping voltammetry. Surface area, Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analysis were used to follow the transformation of ferrihydrite after initial (co)precipitation. Electron microprobe analysis (EMPA) was used to show the distribution of metals within ferrihydrite aggregates. Thermal treatment produced a reduction in soluble Cd2+ and Zn2+, whereas Pb2+ appeared to be expelled from the solid phase. The more stable coprecipitate (formed by slow titration) maintained a constant Cu2+ solubility after thermal treatment. Characterization of the solid phase by XRD indicated that the presence of low levels of metals did not affect the initial or final transformation products, although metals present during the slow titration seemed to stabilize a higher surface area material. The rapid titration resulted in a less ordered (1-line) ferrihydrite than the slow titration (9-line). Furthermore, FTIR analysis indicated that the presence of metals promoted the formation of mixed (microcrystalline) end-products. The initial coprecipitation products seem to determine the final thermal transformation products. These transformation products include ferrihydrite, hematite (Hm), and goethite (Gt)- and lepidocrocite-like microcrystalline structures. Although experimental conditions were favorable for the homogeneous distribution of metals throughout the coprecipitate, EMPA suggests that Cu and Zn segregation within aggregates of Fe oxides occurs.

We applied the hard and soft acid-base (HSAB) model (Xu and Harsh 1990a, 1990b) to bivalent cation exchange on a purified Ca-montmorillonite. As a result, a satisfactory model is proposed to describe the gradual selectivity of exchange with Ca for 4 of the 6 metals studied (Cd, Cu, Pb, Zn). The selectivity is predicted as a function of the differences of electronegativity and softness of the metals. The deviation of Ni and Co data from the predicting model is interpreted in terms of hydration (Ni and Co being the most strongly hydrated ions). The fitting parameters of the model, α and β, are related to the electronegativity and softness characteristics of the surface, respectively. Their ratio gives information on the nature of bonding. Results suggest that covalent bonding modifies electrostatic interactions, which in turn affect selectivity, with an increasing influence of covalent bondings in the order: Pb < Cd < Zn < Cu.

To balance the lack of representativity of the model for the small molar fraction (NM), we propose to associate to the HSAB model an equation describing the variation of the Vanselow selectivity coefficient as a function of the molar fraction of metal on clay.

Hydroxyaluminosilicate (HAS) and hydroxyaluminum (HyA) ionic solutions having final Al concentrations ranging from 3.74 to 4.00 mM; NaOH/Al molar ratios of 1.0, 2.0 and 2.5; and Si/Al molar ratios of 0.00, 0.27–0.30, 0.51–0.56 and 0.95–1.01 were prepared through the interaction of AlCl3, or-thosilicic acid and NaOH solutions. When these solutions reacted with <2 µm sized vermiculite (Vt) and montmorillonite (Mt), varying amounts of Al and Si were fixed on Vt and Mt clays. Potassium fixation and exchange capacities of HyA/HAS (OH/Al = 1.0, 2.0 and 2.5)-Vt and HyA/HAS (OH/AI = 2.0)-Mt complexes were compared with those of untreated Vt and Mt at added K levels ranging from 21 to 319 cmolc kg−1. The untreated Vt clay showed K fixation as high as 94 cmolc kg−1, in contrast to only 16 cmolc kg−1 exchangeable K. The untreated Mt fixed a maximum of 9 cmolc K kg−1 out of a total K adsorption capacity of 67 creole kg−1. In the HyA/HAS-Vt complexes, K fixation reduced drastically in comparison to untreated Vt, and ranged from 9 to 24 cmolc kg−1 out of their total K adsorption capacities of 61 to 81 cmolc kg−1. In the HyA/HAS-Mt complexes, too, the amount of K fixed reduced to a great extent in comparison to Mt and ranged from 1.48 to 1.84 cmolc kg−1. Potassium became more exchangeable due to the presence of hydroxy-interlayers in the clays. The reduction in CEC and the well-known propping effects of hydroxy-cations’ islands in the interlayers might have hindered K fixation by the complexes. The relationships of maximum K fixing capacities of the HyA/HAS-Vt complexes with the amounts of Al, Si and Al + Si fixed on Vt were all exponential and negative. However, the amount of Al + Si or only Al fixed on Vt appeared to be the best indicator of K fixation capacities of hydroxyinterlayered Vt clay.

The sorption capacity of hydrotalcite (HT) and its calcined product (CHT) was evaluated for 131I− sorption from water solution and it was determined as a function of the calcining temperature. The radionuclide content was determined by γ-spectrometry. Solids were characterized by thermal analysis, X-ray diffraction (XRD), electron microscopy and Brunauer-Emmett-Teller (BET) analysis. For 0.1 M Na I solution, labeled with 131I−, sorption capacity was found to be 0.24 meq g−1 (7.2% of the anion exchange capacity, AEC). But, if the sample was previously calcined at 773 K and the HT structure destroyed, the sorption of I− increased considerably, up to 2.08 meq g−1 (63% of the AEC) and the HT structure was reconstructed. The 131I− sorption at very low concentrations (10−14M) was 0.04 × 10−14 meq of 131I− g−1 in the noncalcined HT, but for calcined samples at 773 K, the sorption increased to circa 0.97 × 10−14 meq g−1. Calcination temperature determines the surface area of the resulting mixed oxides, and that property seems to be the most important factor controlling the I− sorption. If the calcination temperature was increased to 873 K, the specific surface area of the oxide mixture increased and I− sorption increased as well, whereas calcination of HT at 973–1073 K resulted in a low surface area and a low I− retention.

Lath-shaped hydrothermal illite particles in Izumiyama pottery stone were examined by contact-mode atomic force microscopy (CMAFM) and tapping-mode AFM (TMAFM) in air. With CMAFM, the lath-shaped particles showed interlacing patterns on the (001) surface in deflection images, while in height images such patterns were unclear. Also, evidence of artifacts caused by frictional forces between the surface and tip and/or edge effects were found in the CMAFM height images of the particle and Si substrate surfaces. In contrast, TMAFM showed interlacing patterns clearly in both amplitude and height images, and artifacts were barely evident. The TMAFM height images permitted the accurate measurement of 1.0- or 2.0-nm height steps corresponding to single or double mica layers, as well.

Many lath-shaped particles in the Izumiyama hydrothermal illite exhibit interlacing patterns on their (001) surface, as shown by these AFM observations. The interlacing patterns are characterized by polygonal spirals with comparatively wide spacings and steps having a height of 1.0 or 2.0 nm. Generally a single lath-shaped particle has a single spiral center on the (001) surface, and 2 mica layers rotated 120° originate from the dislocation point. These support the view that lath-shaped illites belong to the 2M1 polytype. It is likely that these illite particles were formed by a uniform process of development that is characterized by very slow growth, spiral mechanisms in that growth and low supersaturation conditions.

End members and species defined with permissible ranges of composition are presented for the true micas, the brittle micas and the interlayer-cation-deficient micas. The determination of the crystallochemical formula for different available chemical data is outlined, and a system of modifiers and suffixes is given to allow the expression of unusual chemical substitutions or polytypic stacking arrangements. Tables of mica synonyms, varieties, ill-defined materials and a list of names formerly or erroneously used for micas are presented. The Mica Subcommittee was appointed by the Commission on New Minerals and Mineral Names (“Commission”) of the International Mineralogical Association (IMA). The definitions and recommendations presented were approved by the Commission.