Bentonites are candidate materials for high-level radioactive waste (HLRW) repositories and, therefore, are investigated with respect to long-term stability. In order to identify possible bentonite alteration processes, long-term in situ tests are conducted in rock laboratories. The prototype repository in situ experiment (PR) is one of the best examples of this kind of test due to the size of the installation as well as the duration. In the present study, chemical and mineralogical alteration processes of the bentonite MX 80 after an 8 y heating period were investigated. The water content of all samples increased following inflowing Na-Ca-Cl-type granitic groundwater causing cation exchange in the bentonite buffer materials. Exchangeable magnesium was desorbed in the buffer and MgO concentration increased at the bentonite-Cu canister interface; the Mg sink could not be detected, however. CaO also accumulated at this interface mainly as Ca carbonate and Ca sulfate. Cu corrosion products were identified at the bentonite-canister interface by chemical analysis, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM-EDX), and differential thermal analysis. Up to 0.5 mm into the bentonites Cu could be detected by SEM-EDX. No cristobalite dissolution was observed in contrast to other in situ tests in which iron heaters were used. The corrosion products and the lubricant which was added during manufacturing of the bentonite blocks were mixed with the bentonite at the bentonite-canister interface. A quantitative measure of that mixture was the decrease in the cation exchange capacity (CEC). The CEC also reduced in all other samples, however, compared to the CECs of the reference samples, particularly in the warmer deposition hole 5 compared to the colder deposition hole 6. Overall, the PR in situ experiment proved that cation exchange reactions occurred in full-scale bentonite buffer experiments in all bentonite blocks but structural degradation of smectite could not be identified.

Quantitative analysis of clay minerals by X-ray powder diffraction requires oriented clays in order to increase detection limits of the analyses. This is achieved commonly either by smear or sedimentation techniques; however, these techniques can lead to poor analytical precision when used with an internal standard because they often produce non-homogeneous internal standard—clay mineral mixtures. Compaction of bulk shale material at 8000 psi in an hydraulic press produces preferred orientations comparable to that produced by smear or sedimentation. When used with a suitable platy internal standard which provides an estimate of clay mineral preferred orientation, excellent analytical precision is achieved routinely. Several lines of experimental evidence indicate that 1–5 µm MoS2 is an ideal orienting internal standard for use with compaction mounts.

Boron sorption by hydrous Al-oxide was studied as a function of concentration, pH, temperature and in the presence of oxalate and phosphate. For comparison sorption of B was also measured with charcoal as adsorbent.

At constant pH a Langmuir type equation was found to fit the results well at pH values below 7.2 where only boric acid molecules are present in solution. B sorption was dependent on pH with maximum sorption at pH 8.5. Oxalate and phosphate ligands form strong bonds to AI and were found to reduce B sorption. Sorption of boric acid molecules decreased with increasing temperature and the isosteric heat of reaction was 13.8 kJ mol−1. These results indicate that there are two mechanisms of sorption on hydrous Al-oxide, physical sorption of boric acid molecules and ligand exchange (chemisorption) of borate, and both mechanisms are favored onto the oxide.

An attempt is being made to analyze the forces between unit layers of a bentonite particle and between the flat surfaces of two particles from colloid chemical data and theory. The electric double-layer interaction, the van der Waals attraction, and the hydration energies are considered.

From experimental observations the general qualitative shape of the net potential curve of interaction may be derived.

In a quantitative discussion, first the long-range interaction is considered by applying the theory of Verwey and Overbeek in which the net interaction curve is found as the sum of the double-layer repulsion and van der Waals attraction. The fact that the layers do not spontaneously dissociate in solution despite the high charge density of the surfaces points to a considerable specific adsorption potential of the counter ions (the exchangeable ions) to the surface (≈0.2 ev). The consequences for ion exchange are briefly discussed.

Next, two possibilities for the status and position of the counter ions are considered: the cations are either unhydrated and located in or close to the holes in the tetrahedral sheet in six coordination with the oxygen six rings or they are partly or completely hydrated and with their hydration shell adsorbed on top of the oxygen sheet.

Then the short-range interaction of the unit layers is considered. In the case of bentonite there is the fortuitous situation that the net short-range potential curve for the layer interaction can be found experimentally from adsorption isotherms and x-ray diffraction. This net interaction energy is the sum of three contributing energies: the van der Waals attraction, the electrostatic interaction, and the hydration energies. Therefore, on computing the first two for either model mentioned above, the hydration term can be evaluated and its order of magnitude may decide between the two possibilities since ion hydration energy would be expected to be much higher than surface hydration energy.

For the model of unhydrated ions the van der Waals attraction is relatively small and partly compensated by the rather small electrostatic repulsion (repulsion of two finite layers of dipoles). Thus the net repulsion energy measured is practically the hydration energy in this case. This hydration energy figure is of the right order of magnitude if interpreted as hydrogen bonding of a Hendricks water layer to the oxygen surface.

For the model of the at least partly hydrated cations the van der Waals attraction is small, the same as in the first model, but the electrostatic interaction is now an appreciable attraction since the cations take up a midway position between the negative bentonite layers for at least the mono- and dilayer adsorption complex. This makes the computed hydration energy higher; this is readily explained by the availability of the higher ion hydration energy as compared with the surface hydration energy.

Thus the analysis shows both pictures to be acceptable within the limits with which the adsorption isotherms and therefore the net potential curve can be evaluated. More elaborate adsorption data at very low relative humidities would be required to obtain a better estimate of the energies involved in the removal of the last layer of water where the major portion of the ion hydration energy would enter the picture if ion hydration would indeed take place and be the primary cause of interlayer swelling of bentonite.

There is a correlation of bentonite hydration energy with the hydration energy of the counter ions present, but this correlation does not constitute positive evidence of ion hydration. A secondary effect of the ions on the formation of ideal Hendricks’ layers (and thus on their bonding energy to the clay surface), which also depends on ion size, is possible.

Other experimental and theoretical approaches to the problem are briefly mentioned and finally the differences between swelling and nonswelling clays are dealt with.

The hypothesis tested was that macroscopic swelling of montmorillonitic clays is reduced by the presence of interlayer minerals. Fine and coarse clay fractions of Camargo and Panther Greek bentonite samples were artificially interlayered by reaction of Al2(SO4)3 and NaOH in 0∙5% suspensions of the clays. All four clay fractions reacted similarly to artificial interlayering. At an Al:clay ratio of 16 meq Al/g clay the CEC was completely lost, surface area was reduced and X-ray basal spacings were altered. No macroscopic swelling occurred in samples treated with 16 meq of Al/g of clay. At smaller concentrations of hydroxy-aluminum 8 and 2 meq Al/g clay, the clay properties were less drastically altered. Extraction of interlayered clays with Na citrate restored the original C.E.C., surface area, and basal spacings of all samples and resulted in some slight enhancement of C.E.C. and surface areas of the coarse fractions. Treatment with hot Na citrate resulted in an increase in swelling ability but only slight increases in C.E.C. and surface area. Evidence presented supports the hypothesis that macroscopic swelling of montmorillonitic clays is greatly reduced by interlayer materials. Reduced swelling due to interlayering occurs even when other clay properties may be slightly different from those of nontreated samples. Indications are that interlayer material occurs naturally in the clays studied and this may apply to other bentonite deposits.

A complex of vermiculite with ethylene glycol was prepared by repeated boiling of a sodium-saturated cleavage flake in dry ethylene glycol. A stable product with a c period of 12.9 Å afforded 15 terms for a one-dimensional Fourier synthesis. A model composed of glycol molecules with the plane of the zigzag normal to the silicate face is found to be consistent with the observed diffraction data. The complex apparently conforms to a stoichiometric ratio of two molecules per unit cell per layer of vermiculite.

Bentonite- and sepiolite-supported copper catalysts have been prepared either by adsorption of Cu(II) from aqueous solutions of copper nitrate at pH ~4.5 or by adsorption of a [Cu(NH3)4]2+ complex from an ammonia solution of CuSO4 at pH ~9.5. The structure and composition of the calcined preparations have been studied by X-ray diffraction, chemical analysis, and energy dispersive X-rays. Textural characteristics have derived from the analysis of the adsorption-desorption isotherms of N2. All catalysts have been tested for the dehydrogenation of methanol to methyl formate. For this reaction, bentonite-based catalysts were found to have very little activity, which indicates that copper located in the inter-lamellar spaces is inaccessible to methanol molecules. On the contrary, copper-sepiolite catalysts showed a very high specific activity even for those catalysts with a very low copper content. The chemical state of copper in the catalysts on-stream has been revealed by X-ray photoelectron spectroscopy and X-ray-induced Auger techniques. In most of the catalysts Cu+ is the dominant copper species.

The selectivity of K over Ca of Amelia biotite increased sharply upon oxidation by H2O2 at pH 6·0. This increase in K selectivity was only partially reversible upon reduction by Na2S2O4. Oxidation by H2O2 of the Ca-form of this biotite resulted in a loss of no more than 2·8 and 0·4 per cent of the total Fe and Al, respectively, and caused a small and perhaps insignificant decrease in layer charge. Although 95 per cent of the structural Fe2+ of the Ca-form of this biotite was ozidized by H2O2, only 17 per cent was reduced again by four treatments with Na2S2O4.

The evidence indicates that under the conditions of this experiment the loss of protons from structural hydroxyls was the dominant mechanism by which electroneutrality in the biotite was maintained during oxidation of structural Fe2+. Because this mechanism increases the bond strength of interlayer K, it explains the increased K selectivity of biotite upon H2O2 oxidation. The relatively small reduction by Na2S2O4 of structural Fe3+ to Fe2+, which implies an equally small reprotonation of structural hydroxyls, explains the incomplete reversibility of K selectivity by Na2S2O4 treatment.

Natural clay-sized glauconite has the same mineralogical composition as sand-sized glauconite pellets but occurs in <2 μm clay fractions. This particular glauconite habit has been described previously from soil environments resulting from pelletal weathering but is rarely reported in higher-energy sedimentary environments. In the present study, clay-sized glauconite was identified as a common constituent in transgressive Neogene glauconite pellet-rich deposits of the southern North Sea in Belgium. X-ray diffraction results revealed that the characteristics of the clay-sized glauconite are very similar to the associated glauconite pellets in sand deposits. Both glauconite types consisted of two glauconite-smectite R1 phases with generally small percentages of expandable layers (<30%) with d060 values ranging between 1.513 Å and 1.519 Å. Clay-sized glauconite was not neoformed but formed by the disintegration of sand-sized glauconite pellets which were abraded or broken up during short-distance transport within the sedimentary basin or over the hinterland. Even in an environment where authigenic glauconite pellets occur, minimal transport over transgressive surfaces is sufficient to produce clay-sized glauconite. Furthermore, clay-sized glauconite can be eroded from marine deposits and subsequently resedimented in estuarine deposits. Clay-sized glauconite is, therefore, a proxy for the transport intensity of pelletal glauconite in energetic depositional environments and, moreover, indicates reworking in such deposits which lack pelletal glauconite.

The benefits of using kaolin as a source of aluminosilicate in zeolite synthesis to obtain lowercost catalysts, adsorbents, or ion exchangers are widely known. Previous attempts to produce zeolite from natural Iranian kaolin resulted in the formation of zeolites A, X, and HS. Zeolite Y plays an important role in the petrochemical industry due to its application in the area of fluidized catalytic cracking; ~40% of gasoline production is obtained using this process.

In the present study, different methods were used to prepare pure zeolite NaY from the Iranian kaolin available. The effects of different parameters such as aging time, crystallization time, kaolin calcination and crystallization temperature, and starting-material composition were investigated in order to obtain improved properties and maximize phase purity. In all cases, the crystal structure and microstructure were studied using X-ray diffraction and scanning electron microscopy. Among different synthesis approaches, the ‘guide-agent method’ resulted in the formation of zeolite NaY. The synthesis was generally sensitive to changes in kaolin calcination temperature and in hydrothermal synthesis parameters. The optimum parameters to prepare pure zeolite NaY were: kaolin calcination temperature = 680°C, aging time of guide agent = 48 h without an overall gel aging step, and crystallization at 90°C for 36 h.

Lepidocrocite (γ-FeOOH) formation in the hydrothermal brines of the Thetis and Atlantis II Deeps in the Red Sea results in markedly different crystals (size and shape). The only foreign element associated with the crystals is Si and analyses of samples from the two deeps yielded average Si/Fe (molar) ratios of 0.03 and 0.11, respectively. The Si/Fe ratio does not affect formation of a perfect lattice along [010]. Direct observations of crystal morphology as well as X-ray diffraction patterns, Mössbauer and infrared spectra, all indicate that the Atlantis II Deep lepidocrocite is less crystalline than the Thetis Deep lepidocrocite. In one sample a poly-disperse size distribution was resolved indicating a fine-scale variation in precipitation conditions. Infrared spectroscopy suggests that the Si is adsorbed on the lepidocrocite surfaces, probably also forming polymers, as both Fe-O-Si and Si-O-Si bonds can be detected. The formation of the Atlantis II Deep lepidocrocite is due to fast oxidation of Fe2+. The blanket-like layer of lepidocrocite in Atlantis II and Thetis Deeps lepidocrocite was probably formed as a result of precipitation during an abrupt oxidation event of the brine, triggered by down-welling of a condensed oxidized brine, which originated in the northern part of the Red Sea. A difference in Si concentrations determined the different crystal properties of the lepidocrocite formed in the two deeps.

Phenamiphos interacted with homoionic montmorillonites of Ca2+, Mn2+, Co2+, and Ni2+ to form interlayer complexes having basal spacings of about 16.5 Å. In the infrared spectra, the ν-PO bands were displaced towards lower frequencies suggesting that this group interacted with the exchange cations. Moreover, a small shoulder at 1600 cm−1 indicated the partial protonation of the phenamiphos. After heating the complexes to 110°, 160°, and 200°C, however, the bands corresponding to δ-NH2+ and ν-NH intensified because of increased protonation, whereas the ν-PO bands had the same intensity as in pure phenamiphos. The fundamental implication of these observations is that phenamiphos interacts with exchange cations through molecules of coordinated water, possibly by means of the P=O group.

According to Lippmann (1977, 1982) wide compositional variations and excess enthalpies of mixing calculated with electrostatic models imply that clay minerals of variable composition are dis-equilibrium solids. However, recent ATEM analyses of illite samples indicate compositional homogeneity of single illite grains and limited compositional variations in sedimentary basins. Moreover, Lippmann's electrostatic model may be inadequate inasmuch as it neglects polarization energy which is known to be a significant component of lattice energy even in dominantly ionic structures. Contrary to the assumptions of Lippmann, I/S minerals have also been shown to undergo Ostwald ripening.

May et al. (1986) reported that smectites do not reversibly control equilibria and further argued that conceptual and experimental deficiencies inherent in the solubility method prevent the attainment and demonstration of equilibrium in experiments with complex aluminosilicates of variable composition. However, equilibrium may be assumed if: (1) steady states are approached from both under- and over-saturation, (2) the slopes of univariant lines representing mineral-solution equilibria are rational over a wide range of solution compositions and temperature, and (3) results are reproducible in experiments of long duration. Recent solubility studies of smectites, chlorites, and illites meet these criteria indicating that clay minerals of variable composition are true phases capable of attaining equilibrium.

Interlayer K was extracted with sodium tetraphenylboron solution from a powdered sericite heated to the temperature of dehydroxylation and quenched to room temperature. By this procedure, sericite of the 2M1 type was changed to an interstratified mineral. The X-ray diffraction properties of this interstratified mineral are similar to “rectorite”.

Polycarboxylate superplasticizer (PCE) is a widely used water-reducing agent that can reduce significantly the water demand of concrete, which reduces the porosity and enhances the strength and durability of the concrete. (The PCE consists of a single backbone with many long PEO side chains.) Generally, aggregate occupies >70 wt.% of concrete; clay minerals are ubiquitous in nature and are difficult to avoid in mined aggregates. Clay minerals in aggregate often render the PCE ineffective and give rise to rapid loss of the fluidity of the concrete; this phenomenon is referred to as ‘poor clay tolerance of PCE.’ Though the poor clay tolerance of PCE is known widely, the relationship between the clay tolerance and the molecular structure of the PCE, in particular the effect of the side-chain structures, on clay tolerance is not understood completely. The objective of the present study was to determine the effect of different grafting densities of polyethylene oxide (PEO) side chains on the clay tolerance of PCE. The raw materials included mainly PCE, which was synthesized using acrylic acid and isopentenol polyoxyethylene ether, and a natural montmorillonite (Mnt), one of the most common clay minerals. The loss of fluidity of the cement paste was tested to assess the clay tolerance; total organic carbon was used to measure the amount of PCE adsorbed; X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermogravimetric analysis were used to investigate the microstructure of the intercalated Mnt. The results showed that preventing the superficially adsorbed PCE from being intercalated into Mnt was of great importance in terms of the improvement in clay tolerance of PCE, which increased with greater grafting density of PEO in the side chain of the PCE. The results also suggested the possibility that polymers which intercalate preferentially into the Mnt could improve significantly the clay tolerance of the PCE system.

Pennsylvanian underclay from Illinois is characterized by well-developed mineral zonation: towards the coal bed, marly limestone gradually evolves into carbonate-free clay, chlorite becomes undetectable and illite/smectite changes from ordered and illite-dominated into random and smectite-dominated, with both types present in the middle of the profile. Transmission electron microscopy (TEM) observations of the bulk material imply that disappearance of calcite is due to dissolution. Movement of SiO2 in the upper part of the profile is evidenced by quartz cementation of clay aggregates; crystallization of kaolinite, by the presence of vermicular aggregates absent from less-altered samples. Illitic material in unaltered (limestone) samples consists of rare, large, Al-rich crystals of mica, interpreted as detrital, and abundant thin crystals of illite/smectite intimately mixed in approximately equal proportions with even thinner crystals of discrete illite. Both are more Mg- and Fe-rich than the large mica crystals and are interpreted as diagenetic, based on their 1Md polytype and the correlation with coal rank. Illitic material of the upper, carbonate-free section of the profile contains the same 3 types of crystals, but in different proportions: illite/smectite crystals dominate and their composition is more smectitic. Two distinct morphologies of the aggregates of crystals with different proportions of the component layers are observed. It explains why 2 different illite/smectites are detectable by X-ray diffraction (XRD) in these samples. The analysis of chemical data suggests that the underclay is a residue after dissolution of all of the calcite and half of the quartz from the original limestone (paleosol and/or telogenetic process). The TEM observations are not decisive regarding the origin of variation within the illitic material. It may result from burial diagenetic illitization of more-smectitic material, similar to the composition preserved in the center of underclay profile, or it may represent telogenetic alteration of illitic clay by acid waters penetrating down from the coal bed. The aggradation model explains the increase in percent K2O, MgO and illite layers in the uppermost part of the profile. Whichever is the direction of reaction, it proceeds on an aggregate-by-aggregate basis and not fundamental particle-by-particle, and cannot be explained by simple opening or collapse of interlayers.

Quaternary debris flows derived from ophiolite melange in northern Southland, New Zealand, are locally cemented and veined by cross-fiber and fine-grained chrysotile. Chrysotile was identified by optical, X-ray powder diffraction, electron microprobe, differential thermal (DTA), and infrared analysis methods. Microprobe and DTA also suggested the presence of as much as 6% of sub-microscopic, noncrystalline alumina, probably in the form of pseudoboehmite. Cavity fillings and irregular veins containing chrysotile are as thick as 40 cm and commonly contain lizardite clasts. Calcite commonly accompanies chrysotile as a vein mineral. Magnetite and pyrite are found near and adjacent to chrysotile veins. These accessory minerals imply that the chrysotile formed under alkaline, reducing conditions. Surface water seepages have pH = 9. Remnant debris-flow topography, Holocene radiocarbon dates, and the absence of hot spring activity confirms that chrysotile can form under near-surface, low-temperature conditions. Growth of chrysotile fibers on a lizardite substrate suggests that the chrysotile formed by solution of detrital lizardite and subsequent precipitation in cavities within the debris flow.

Two diagenetic stages of zeolitic alteration were recognized in a study of a thin bed of rhyolitic ash that was deposited in Eocene Lake Gosiute (Laney Member of the Green River Formation). The ash bed can be traced for 30 km along strike and represents a single volcanic event. The bed was not buried deeply (<100°C), and originally it was compositionally homogeneous. Initially, the bed altered to clino-ptilolite, heulandite, an intermediate phase between these two zeolites, and mordenite. These early reactions involved the hydration and solution of glass by saline, alkaline solutions and the subsequent precipitation of zeolites. The variation in zeolite mineralogy is due to differences in interstitial fluid chemistry that resulted from either fluctuations in lake-water chemistry or the proximity of spring discharge. These reactions, exclusive of the addition of H2O, involved only minor amounts of mass transfer over very small distances. Later, after burial, the early-formed zeolites reacted with upward moving sodium carbonate brines that were produced by dewatering of underlying evaporite deposits. The sodium carbonate brines, in equilibrium with trona and nahcolite, elevated the activity of Na+ and produced analcime. These later dehydration reactions involved significant mass transfer.

The characterization of magnetic minerals and the relationship of these minerals to the magnetic susceptibility of soils that have developed on various parent materials can provide valuable information to various disciplines, such as soil evolution and environmental science. The aim of the study reported here was to investigate variations in the magnetic susceptibility (χ) of soils in western Iran due to differences in lithology and to examine the relationship of χ to ferrimagnetic minerals. Eighty samples were collected from eight parent materials taken from both intact rocks and associated soils. The soil parent materials included a range of igneous and sedimentary rocks, such as ultrabasic rocks (Eocene), basalt (Eocene), andesite (Eocene), limestone (Permian), shale (Cretaceous), marl (Cretaceous), and the Qom formation (partially consolidated fine evaporative materials, early Miocene). The 80 samples were analyzed for χ using a dual-frequency magnetic sensor and for mineralogy using X-ray diffraction (XRD). The highest χ values were found in the ultrabasic rocks and associated soils, while the lowest χ values were observed in the limestone rocks and associated soils. The pedogenic processes significantly enhanced the χ values of soils developed on the sedimentary rocks due to the formation of ferrimagnetic minerals. In contrast, χ values decreased as a result of pedogenic processes in soils developed on igneous rocks due to the dilution effects of diamagnetic materials, such as halite, calcite, phyllosilicates, and organic matter. The significant positive correlation between the XRD peak intensity of the maghemite/magnetite particles and χ values confirmed that χ values in soils are largely controlled by the distribution and content of ferrimagnetic minerals. These results show that χ measurements can be used to quantify low concentrations of ferrimagnetic minerals in the soils of semiarid regions.